Improvement of spills and related improvements, as well as their treatment.

Abstract

The use of polyferric sulfate (PFS) or ferric sulfate (FS); and sulfuric acid (SA) in combination to treat liquid animal runoff and / or sludge (i.e., combined treatment) to reduce methane emissions from liquid animal runoff and / or sludge (i.e., combined treatment) compared to untreated liquid animal runoff and / or sludge.

Description

Technical Field

[0001] The present invention relates to improvements relating to effluent and its treatment. In particular, reducing methane emissions from animal effluent and related thereto. The present invention may also have utility for simultaneously reducing hydrogen sulfide release from effluent.

Background Art

[0002] Here, the present invention is mainly for the sake of facilitating explanation in relation to dairy farm effluent treatment systems. However, the present invention can have good applicability to other sources of animal effluent, and such discussions should not necessarily be regarded as limiting.

[0003] The storage of animal effluent on dairy arms presents several important problems including the emission of methane gas (CH4), a powerful greenhouse gas having a 100-year global warming potential 28 times that of carbon dioxide.

[0004] The use of animal effluent storage ponds for manure management has increased in proportion to new zealfar dairy arms; c. 5% in 1990 - c. 81% in 2017 (MPI 2017). This increase in the use of storage ponds has been carried out in the following order.

[0005] (i) Capturing and storing effluent from off-paddock structures (e.g., milking parlors, feeding pads, stand-off pads); (ii) Enabling the deferral of overland irrigation of effluent until the risk of punching and / or outflow to rivers and lakes is avoided (commonly referred to as "extended washout").

[0006] Regional authorities (regional councils) are promoting / requiring dairy farmers to construct effluent ponds that provide large storage capacities (in some cases up to 3 months of storage) in order to reduce the risk of effluent that must be applied to land during wet conditions.

[0007] However, an "unintended consequence" of increasing the number and size of animal runoff storage ponds is a greater risk of methane emissions contributing to climate change.

[0008] This data, published in greenhouse gas inventory form, shows the increase in greenhouse gas emissions from fertilizer management, which rose by 121% from 720.7 kt CCh-e in 1990 to 1,596.8 kt CCh-e in 2017 (MFE, 2019a).

[0009] The majority (>90%) of greenhouse gas emissions from the fertilizer management category are in the form of methane gas produced during the storage and management of agricultural milk runoff. When runoff is stored in ponds, the organic matter in the runoff anaerobically produces methane gas. In 2017, methane emissions from 1,475.1 kt CCh-e in the fertilizer management contribution represent 92.4% of the fertilizer management category (MFE, 2019a). The remaining 121.6 kt CCh-e (7.2%) is nitrous oxide produced by nitrification and denitrification processes (i.e., <8% of the fertilizer management category).

[0010] In 2017, fertilizer management contributed 4.1% of greenhouse gas emissions from the All New Zealpha agricultural sector, making it the third largest GHG category after enteric fermentation and agricultural soil categories. However, since the majority of runoff storage ponds are built on milk arms, fertilizer management is estimated to account for approximately 7-10% of methane emissions from milk arms (MPI, 2012; Labach et al., 2015).

[0011] New Zealpha and Ministry for Environmentally Interactive GHG Stocks (MFE, 2019a) shows that in 2017, the amount of methane released from dairy cow manure ponds was equivalent to 1,255 kt CCh-e, and the amount of methane released from dairy cow enteric fermentation was equivalent to 13,560 kt CCh-e. Therefore, the total amount of methane released from New Zeraland dairy farms was equivalent to 14,815 kt CCh-e, of which 8.5% came from manure management (i.e., ponds).

[0012] Therefore, it would be useful to devise an animal runoff treatment system that can reduce the risk of methane emissions from animal runoff, particularly from animal runoff storage ponds.

[0013] As detailed in WO 2021 / 071367A1, the inventors have previously devised treatments using ferric sulfate (PFS) or ferric sulfate (FS) to significantly reduce methane emissions.

[0014] However, PFS and FS, which yield excellent results, are relatively expensive chemicals, as shown in the following examples.

[0015] A typical cost example of PFS or FS is its use as a sole treatment agent for liquid animal spills. Current PFS or FS cost c. = $1.40 / L Average NZ dairy farm effluent = 400cows x 70L / cow / day x 270 days = 7560000L pa PFS rate to reduce methane emissions = 1.56 L / 1000 L FDE (250 mg Fe / L) Volume requirement = 1.56L x 7 = 560m³ = 11 = 794L @ $1.40 / L = $16,511pa [Prior art documents] [Patent Documents]

[0016] [Patent Document 1] WO 2021 / 071367A1 [Overview of the project] [Problems that the invention aims to solve]

[0017] Therefore, there remains a need to reduce the costs associated with mitigating methane in dairy farm runoff ponds and other similar areas, increase the adoption of this new technology, and avoid negatively impacting farmers who are helping to combat climate change.

[0018] Sulfuric acid can be used to treat the effluent.

[0019] A representative cost example of sulfuric acid (SA) is as the sole treatment agent for liquid animal effluent.

[0020] Current SA cost = c. $0.5 / L Average NZ dairy farm effluent = 400 cows x 70 L / cow / day x 270 days = 7,560,000 L pa Methane emissions = equivalent SA dosage rate to mitigate 1.56 L / 1000 L FDE Volume required = 1.56 L x 7,560 m = 11,794 L @ $0.5 / L = $5,897 pa 3

[0021] There may also be further advantages if a more cost-effective treatment for reducing methane emissions from liquid animal effluent and / or sludge can be provided than treatment with PFS or FS alone, or SA alone.

[0022] It would also be advantageous if a more effective treatment for reducing methane emissions from PFS or FS alone, or SA alone, than from liquid animal effluent and / or sludge can be provided.

[0023] It would also be useful if alternative methods for reducing methane emissions in discharge ponds etc. can be provided.

[0024] It is also an advantage to ensure that there is at least no increase in toxic hydrogen sulfide gas emissions such as would occur if sulfuric acid were used by itself to treat the waste liquid.

[0025] Furthermore, in addition to reducing methane emissions, there is the advantage that the treatment can also reduce hydrogen sulfide emissions from discharge ponds etc.

[0026] Furthermore, it is useful when a treatment formulation having viscosity can be provided, and this viscosity allows the treatment to be pumped or injected.

[0027] The object of the present invention is to address the aforementioned problems of methane gas and / or hydrogen sulfide emissions, or at least to provide a publicly useful alternative. [Means for solving the problem]

[0028] All references, including any patents or patent applications cited herein, are incorporated herein by reference. No reference is permitted to constitute prior art.

[0029] Throughout this specification, the terms “comprise,” or variations thereof such as “comprises,” or “comprising,” shall be understood to mean the inclusion of the element, integer, or step, or group of integers or steps of elements, but the exclusion of any other element, integer, or step, or group of elements, integers, or steps.

[0030] Further aspects and advantages of the present invention will become apparent from the following description, which is given merely as an example.

[0031] definition "Farm milk runoff (FDE)" and "liquid agricultural water runoff," as well as "liquid animal runoff" and "liquid animal runoff," and "sewage" and "slurry" all refer to animal urine and feces that have been rinsed from yards, milking holes, barns, or other animal confinement areas and contain liquid (i.e., water) and solid matter mixed therein.

[0032] As used herein, the term "sludge" refers to a viscous, semi-solid material formed from liquid animal effluent that is present over time at the bottom of an effluent pond or effluent storage tank.

[0033] As used herein, the term "ORP" or "redox potential" refers to the tendency of chemical species (molecules) in the effluent to gain or lose electrons, and is measured in mV. A low redox potential value (e.g., a negative mV value) indicates the presence of anaerobic conditions and a tendency for reactions in the effluent to decrease certain molecules (e.g., ferric (Fe)). 3+ ) is First Iron & Steel (Fe 2+ ) or carbon dioxide (CO2) is reduced to methane (CH4).

[0034] The term "anaerobic" as used here refers to the absence of oxygen in the effluent of liquid animals to a degree that favors microorganisms classified as anaerobic.

[0035] As used herein, the term "aerobic" refers to the presence of oxygen in liquid animal effluent, insofar as it favors microorganisms classified as aerobic.

[0036] As used herein, the term “agent” refers to an element, compound, or mixture thereof, or a mixture thereof, which may be in the form of a powder, crystal, gas, liquid, or solute.

[0037] As used herein, the term “concentrated sulfuric acid” typically refers to 90%–98% F SCUs, preferably c. 96% H₂SO₄ and c. 4% H₂O, which is 18 moles of sulfuric acid per liter.

[0038] As used herein, the term “dilute sulfuric acid” refers to sulfuric acid having concentrations ranging from substantially 33%–80% (i.e., substantially 64% H2O and 33% H2SO4 UP) to substantially 20% H2O and 80% H2SO4 UP.

[0039] As used herein, the term “substantially” refers to an amount that, unless otherwise required, may differ literally from the stated value or range, but is still within a margin of variation acceptable to a person skilled in the art, in order to be able to work to achieve the objective of the claimed invention, despite the stated amount used in the claims (i.e., the literal boundary). For clarity, being within 1% or 6% to 10% of the amount stated in the claims should be understood as achievable unless there is a strict compliance with the amount deemed essential to achieve the invention. Accordingly, any claim of the invention should be evaluated within the context of this definition unless the data in the specification support and / or prior art require a narrower or more literal view of the amount stated in the claim.

[0040] The terms "PFS / FS" or polyferric sulfate (PFS) / ferric sulfate (FS), when used herein, should be understood to mean PFS and / or FS, respectively.

[0041] According to a first aspect of the present invention, the following uses are provided. Ferric polysulfate (PFS) / Ferric sulfate (FS) -Sulfuric acid (SA) Combined treatments for liquid animal runoff and / or sludge (i.e., combined treatment) reduce methane emissions from liquid animal runoff and / or sludge compared to untreated liquid animal runoff and / or sludge.

[0042] It should be understood that while the data contained herein relate only to FS-only PFS, nothing prevents the use of mixtures of FS and PFS for treating spills according to the present invention.

[0043] Preferably, the use of SA and PFS / FS substantially as described above may have a dose rate calculated from the measurement of the redox potential of the liquid animal effluent and / or sludge.

[0044] Preferably, the use of SA and PFS / FS as described above may substantially comprise a combined treatment in which, after about 50% or more of the liquid animal spillage has been removed from the location where the liquid animal spillage is being held, a sulfuric acid (SA) is added to the stored liquid animal spillage to reduce the amount of ferric sulfate (PFS) or ferric sulfate (FS), and sulfuric acid (SA) necessary for the first treatment of the spillage and / or sludge.

[0045] Preferably, the use of SA and PFS / FS can reduce methane emissions. Compared to untreated sludge and / or untreated liquid animal spills, From the sludge, and / or from the sludge The liquid animal runoff includes any further untreated liquid animal runoff that enters the pond over a period of at least one month, including any further untreated liquid animal runoff that includes any further untreated liquid animal runoff.

[0046] Preferably, the use of SA and PFS / FS as substantially described above may be used to increase the redox potential of liquid animal effluent and / or sludge.

[0047] Preferably, the oxidation-reduction potential (also known as the oxidation-reduction potential - ORP value) can be measured using a Thermo pH 6+ pH / ORP meter (CO1X 245026W) having a 12 x 90 mm double-junction gel-filled ORP electrode plastic body with a 5 m BNC connector cable (ECFC 7960205B) supplied by Thermo Fisher Scientific NZ Limited. This ORP meter has an accuracy of + / -lmV. This is how the oxidation-reduction potential was measured in the examples detailed in the specification and figures of this application. However, it should be understood that other ORP probes are available and suitable for the present invention.

[0048] According to a second aspect of the present invention, the use of a combined treatment that raises the oxidation-reduction potential to above 0 mV is provided.

[0049] Preferably, the oxidation-reduction potential can be raised to 100 mV.

[0050] In general, liquid animal spills and / or sludge may be retained as follows: pond sauce; Lagoon tank or Storage or transport containers

[0051] According to a third aspect of the present invention, the use of substantially the above-described combination processing is provided, where PFS / FS and SA may be as follows: To liquid animal spills and / or sludge, they are added sequentially or simultaneously, separately or at the same time. They are mixed together immediately before adding the LAE and / or sludge.

[0052] Preferably, when PFS / FS and concentrated SA are mixed together, this is substantially within 10-20 seconds, or substantially within lm-5m when introduced into the pond or wastewater holding area. The inventors of PFS / F S and S A The inventors discovered that the mixture can become viscous and paste-like for a period of time, and / or solid, which can be difficult to deliver through pump and pipe systems.

[0053] According to a fourth aspect of the present invention, a combined treatment is provided for reducing methane emissions from liquid animal effluent and / or sludge compared to untreated liquid animal effluent and / or untreated sludge: Sulfuric acid (SA) component Polyferric sulfate (PFS) / Ferric sulfate (FS) components

[0054] Preferably, substantially the above-described combination processing is provided, where the ratio of the SA component to the PFS / FS component may be substantially in the range of 29:71 to 50:50.

[0055] Preferably, the PFS / FS concentration may be substantially in the range of 50 mg Fe / L to 100 mg Fe / L.

[0056] It should be noted that throughout all aspects of the present invention outlined herein, the concentration of PFS / FS may be substantially in the range of 50 mg Fe / L to 100 mg Fe / L.

[0057] A seventh aspect of the present invention provides a method for reducing methane emissions from liquid animal effluent, the method comprising the step of raising the oxidation-reduction potential of liquid animal effluent and / or sludge in a pond from -200mV or less to greater than 0mV.

[0058] Preferably, the above method raises the redox potential of the liquid animal effluent to above 100 mV.

[0059] Preferably, the above method achieves a reduction in methane emissions of at least substantially 90% compared to untreated liquid animal spills.

[0060] According to an eighth aspect of the present invention, a method for reducing methane emissions is provided, which includes the step of adding both. Sulfuric acid (SA) Ferric polysulfate (PFS) / Ferric sulfate (SA) Liquid animal spills and / or sludge

[0061] Preferably, the percentage ratio of SA to PFS / FS in the above methods, uses, and combined processing is substantially between 29%SA and 50%SA.

[0062] According to a ninth aspect of the present invention, the following uses are provided. a) Ferric polysulfate (PFS) / Ferric sulfate (FS) b) Sulfuric acid (SA) Treat the liquid animal runoff and / or sludge to reduce the liquid animal runoff and / or sludge simultaneously compared to untreated liquid animal runoff and / or sludge.

[0063] A tenth aspect of the present invention provides a method for reducing methane and hydrogen sulfide emissions from liquid animal waste, comprising the following steps. Sulfuric acid (SA) Ferric sulfate (FS) / Polyferric sulfate (PFS) With respect to the aforementioned liquid animal effluent and / or sludge,

[0064] According to an eleventh aspect of the present invention, a transformation of liquid animal effluent and / or sludge from anaerobic to aerobic conditions is provided to reduce the emissions of methane and / or hydrogen sulfide from untreated liquid animal effluent and / or sludge, which is provided by creating an aerobic environment that is hostile to methane-producing substances residing on or in the sludge in runoff ponds or other runoff repositories.

[0065] According to a twelfth aspect of the present invention, the use of the following combination processing is provided. Ferric polysulfate (PFS) / Ferric sulfate (FS) Sulfuric acid (SA) Increases the redox potential of liquid animal effluent and / or sludge.

[0066] Preferably, a combination of PFS / SA and sulfuric acid is used to raise the redox potential above 0mV in order to substantially increase the redox potential as described above.

[0067] According to a thirteenth aspect of the present invention, the use of sulfuric acid and PFS / FS is provided to increase the redox potential, while the acidification level of the effluent and / or sludge remains substantially above pH 4.

[0068] According to a fourteenth aspect of the present invention, the use of a combination of concentrated sulfuric acid (SA) and polyferric sulfate (PFS) / ferric sulfate (FS) is provided for treating liquid animal effluent, wherein the dosage of the SA+PFS / FS combination is substantially 0.468 ml / L of liquid animal effluent and / or sludge, and the amount delivered is as required to achieve an oxidation-reduction potential above 0mV.

[0069] A method for reducing methane emissions from stored liquid animal effluent and / or sludge compared to untreated liquid animal effluent or untreated sludge is provided, comprising the following steps. a) Step S S / F S Determine one of the following and add it to the spilled material along with SA to form a treatment. b) Add and mix with the liquid animal effluent or sludge in an effective amount from step a) in order to increase the redox potential of the liquid animal effluent / sludge above 0mV.

[0070] According to a sixteenth aspect of the present invention, the use of oxidation-reduction potential is provided for determining the following: A quantity for the initial treatment of liquid animal spills or sludge, and / or Is the initial processing dose effective? When liquid animal spills or sludge are treated using a combination of PFS / FS and SA treatment to reduce methane emissions from untreated spills or sludge.

[0071] According to a 17th aspect of the present invention, a method for treating sludge related to liquid animal spills is provided, comprising the following steps: a) Treat liquid animal effluent to increase its oxidation-reduction potential substantially from below -200mV to above 0mV.

[0072] According to an eighteenth aspect of the present invention, a processing and mixing apparatus is provided which includes the following: a) A first pump that is fluid-connectable to a first conduit or capable of fluid communication with an outflow pond or tank; b) A second pump associated with a concentrated SA source and a second fluid conduit; c) A third pump having a polyferric sulfate (PFS) / ferric sulfate (FS) source and a third fluid conduit. d) Including mixing chamber / manifold The inlet connected to the pump delivers the effluent to the chamber / manifold. Exit port Here, the PFS / FS supply source is in fluid communication with the mixing chamber / manifold via the second and third pumps / conduits, respectively, so that the second and third pumps can deliver SA and PFS / FS to the chamber / manifold, and the mixing chamber / manifold is adapted to be connectable to and disconnectable from conduits that can return the treated effluent to the pond.

[0073] Preferably, the chamber / manifold may include oxidation-reduction potential (ORP) sensors and / or pH sensors connected to appropriately programmed PLUs that control the operation of each pump.

[0074] A further aspect of the present invention provides a truck or other vehicle that includes substantially the processing and mixing apparatus described above.

[0075] Preferably, as substantially as described above, the ratio of the SA component to the PFS or FS component may be substantially in the range of 29:71-50:50.

[0076] According to a 19th aspect of the present invention, the use of SA and PFS / FS substantially as described above is provided to reduce methane emissions. From the sludge, and / or from the sludge From liquid animal runoff containing any further untreated liquid animal runoff, including any further untreated liquid animal runoff entering the pond for a period of at least one month. Compared to untreated sludge and / or untreated liquid animal runoff

[0077] According to a 20th aspect of the present invention, a composition comprising the following is provided. Liquid animal spills and / or sludge Sulfuric acid and PFS / FS

[0078] Preferably, the composition may have a pH of substantially 4.

[0079] The above-mentioned composition, wherein the oxidation-reduction potential of the composition is substantially above 0 mV.

[0080] The oxidation-reduction potential of the above compositions is substantially between 0 mV and 100 mV.

[0081] According to a 21st aspect of the present invention, a composition comprising the following is provided. Liquid animal spills and / or sludge Sulfuric acid and PFS / FS The oxidation-reduction potential of the composition is substantially between 0 mV and substantially 100 mV.

[0082] According to the 22nd aspect, substantially the above-described use, method, or combination of processing is provided, which shifts the redox potential of the composition substantially from substantially -200mV to substantially 0mV to substantially 100mV.

[0083] According to the 23rd aspect, a treatment composition comprising the following mixture is provided. Dilute sulfuric acid (SA) Ferric polysulfate (PFS) / Ferric sulfate (FS)

[0084] Preferably, the mixture of diluted SA and PFS / FS is a 50:50 mixture.

[0085] In some embodiments, the diluted SA has a concentration of substantially 50%.

[0086] Preferably, the diluted SA has a concentration of substantially 33%.

[0087] According to the 24th aspect, the use of substantially the treatment composition described above is provided for treating liquid animal runoff and / or sludge to reduce methane emissions therefrom, compared to untreated liquid animal runoff / sludge.

[0088] According to the 25th aspect, a use / method is provided for modifying the redox potential of a liquid animal effluent by substantially using the treatment composition described above such that the redox potential is substantially 0 mV or higher.

[0089] According to a 26th aspect of the present invention, a processing apparatus for treating liquid animal spills is provided. a) Source of the processing composition and related pumps b) A conduit that is connected to the pump to create a fluid communication state, or a conduit that can be created to create a fluid communication state, and is connected to an outflow pond or tank.

[0090] Further aspects of the technology to be considered in all novel embodiments will become apparent to those skilled in the art by reading the following description, which provides at least one example of a practical application of the technology.

[0091] The following is not intended to limit the scope of one or more embodiments of this technology by reference to the following drawings. [Brief explanation of the drawing]

[0092] [Figure 1]Figure 1 shows that PFS + concentrated sulfuric acid, when both are added to liquid animal effluent, is highly effective in reducing methane flux by more than 90% and is more effective than PFS alone over the long term (FDE = untreated agricultural milk sap effluent). PFS = effluent treated with PFS at a rate of 250 mg Fe / L FDE. PFS + SA 50 = effluent treated with PFS with 50 mg Fe / L FDE (0.31 ml / L) + 0.31 ml / L sulfuric acid SA. PFS + SA 75#1 = effluent treated with PFS at a rate of 75 mg Fe / L (0.47 ml / L), and sulfuric acid at a similar rate of 0.47 ml / L. PFS + SA 75#2 = effluent treated with PFS with 75 mg Fe / L (0.47 ml / L) + sulfuric acid at a rate of 0.38 ml / L. [Figure 2] Figure 2 shows that PFS + concentrated SA is more effective than PFS alone in raising the initial redox potential of the treated effluent when both are added to liquid animal effluent, thus creating aerobic conditions in which the methane source cannot survive (symbols are as described above). [Figure 3] Figure 3 shows the dose-response relationship between PFS + concentrated sulfuric acid and pH (symbols are as described above) when both are added to liquid animal effluent. [Figure 4]Figure 4 shows that the concentration of toxic hydrogen sulfide gas was highest when effluent was treated with concentrated sulfuric acid (SA) alone compared to PFS and / or ferric sulfate (FS) used in combination with SA (FDE = untreated agricultural dairy effluent; PFS = effluent treated with PFS with 225 mg Fe / L FDE (1) + 4 ml / L FDE); SA = 0.42 ml / L FDE with sulfuric acid alone; PFS / SA 67.5 = effluent treated with PFS with 67.5 mg Fe / L FDE (0.4 ml / L) + 0.38 ml / L sulfuric acid SA; FS / SA 67.5 = effluent treated with ferric sulfate (FS): 67.5 mg Fe / L (0.5 ml / L) + effluent treated with 0.42 ml / L sulfuric acid). The peak hydrogen sulfide gas concentration released for SA treatment alone (41 ppm) is the acceptable 8-hour exposure time for this gas (5 ppm). This is eight times the Weighted Average (TWA) concentration and four times the Short Term Exposure Limit (STEL) concentration for 15 minutes of exposure to this gas (10 ppm), while the hydrogen sulfide concentration in all other treatments, including PFS or FS, along with SA, remains below the critical 5 ppm concentration (Reference: https: / / www.worsafe.gov.nz / topo-and-industry / monitoring / workplace-exposure-standard-and-biological-exposure-index / all-substances / view / hydrogen-sulfides). [Figure 5] Figure 5 shows that a dual dose of PFS and concentrated sulfuric acid is more effective in reducing methane emissions than PFS alone, and that the effect can be applied over 2 months - (FDE = untreated agricultural sap effluent). PFS 225 is effluent treated with PFS at a rate of 225 mg of Fe / L FDE (1.4 ml / L FDE). SA = sulfuric acid (SA) alone at 0.42 ml / L FDE; PFS / SA 67.5 = effluent treated with PFS with 67.5 mg of Fe / L FDE (0.4 ml / L) and then 0.38 ml / L of sulfuric acid SA is added; FS / SA 67.5 = effluent treated with ferric sulfate (FS) at 67.5 mg of Fe / L (0.5 ml / L) + sulfuric acid at 0.42 ml / L). [Figure 6]Figure 6 shows the dual treatment of FDE with PFS + concentrated sulfuric acid, resulting in a significant 99% reduction in the total amount of methane released from FDE over a two-month period. Treatment of FDE with ferric sulfate + sulfuric acid also resulted in a 99% reduction in the total amount of methane released over a two-month period. Both of these treatment mixtures were more effective than PFS alone (61% reduction) or SA alone (96% reduction) (FDE = agricultural dairy product effluent). PFS 225 = PFS applied at a rate of 225 mg Fe / L; SA = sulfuric acid (SA) alone with 0.42 ml / L FDE; PFS / SA 67.5 = effluent treated with PFS with 67.5 mg Fe / L FDE (0.4 ml / L) and 0.38 ml / L sulfuric acid SA added; FS / SA 67.5 = effluent treated with ferric sulfate (FS) with 67.5 mg Fe / L (0.5 ml / L) + sulfuric acid at 0.42 ml / L). [Figure 7] Figure 7 shows a strong relationship (R=0.9943) between the dose rate of PFS + sulfuric acid binding treatment and sulfuric acid binding treatment of wastewater, as well as an exponential decrease in methane emission flux with increasing treatment additive rates. Methane emission flux was reduced by more than 99% at treatment rates exceeding 100 mg Fe / L FDE, 96% at 75 mg Fe / L FDE, and 91% at 50 mg Fe / L FDE. [Figure 8] Figure 8 shows that double treatment of FDE with PFS + sulfuric acid additive and double treatment with 0.75 ml PFS / L FDE (c. 150 mg Fe / L) + 0.3 ml H2SO₄ / L FDE (ratio of sulfuric acid to PFS) + 0.3 ml H2SO₄ / L FDE (ratio of sulfuric acid to PFS) significantly reduced the methane emission flux from treated effluent (TE) over 53 days compared to untreated FDE. [Figure 9] Figure 9 shows that double treatment with FDE containing PFS + sulfuric acid additive and with 0.75 ml PFS / L FDE (c. 150 mg Fe / L) + 0.3 ml H2SO4 / L FDE (ratio of sulfuric acid to PFS) + 0.3 ml H2SO4 / L FDE (ratio of sulfuric acid to PFS) significantly reduced the total amount of methane released from the treated effluent (TE) by 90% compared to untreated FDE. [Figure 10] Figure 10 shows that by treating the agricultural dairy product runoff "sludge" from the bottom of the runoff pond containing PFS + sulfuric acid, methane emissions from the "sludge" can be significantly reduced, and it shows the difference from fresh FDE added to the tank over 85 days (SL UFDE = untreated sludge + fresh FDE added, SL TFDE = sludge treated with 0.47 ml / L of PFS and sludge treated with 0.47 ml / L of SA). [Figure 11] Figure 11 shows that treating the "sludge" from the bottom of an outflow pond containing PFS + sulfuric acid can significantly reduce the total amount of methane released from the "sludge" + fresh FDE, which is 97% added to the sludge. [Figure 12] Figure 12 shows a schematic diagram of a processing and mixing apparatus according to a further aspect of the present invention. [Figure 13] Figure 13 shows a schematic diagram of one preferred embodiment of a processing and mixing apparatus as shown in Figure 12. [Figure 14] Figure 14 shows a photograph of a clear glass bottle containing a 50:50 mixture of concentrated SA and PFS. [Figure 15] Figure 15 shows a photograph of a clear glass bottle containing a 50:50 mixture of diluted (33%) SA and PFS. [Figure 16] Figure 16 shows the effectiveness of a new treatment composition containing a 50:50 mixture of PFS solution and diluted (33%) sulfuric acid in reducing methane emissions. [Modes for carrying out the invention]

[0093] Further aspects of the present invention will become apparent from the following description, given with reference to the accompanying drawings, merely as examples.

[0094] In the drawings, the units for methane gas emissions are presented in carbon dioxide equivalents, as these are standard units used in the new Zealpha and national stocks for greenhouse gas emissions (MFE, 207b), and taking into account the fact that methane has a global warming potential 28 times greater than that of carbon dioxide.

[0095] Therefore, the "methane emission flux" (i.e., the mass of methane emitted per unit area per unit time) is expressed in units of "mg CO2-e / m / h", and the "total amount of methane emission" over the measurement period is expressed in units of "kg CCh-e / ha" (or g CCh-e / m).

[0096] Experiment #1 A column study of a simulated animal runoff pond was conducted to determine the effects of adding various mixtures of ferric sulfate (PFS) and PFS + concentrated sulfuric acid to treat agricultural and dairy wastewater collected from farms. The experiment consisted of PVC pipes (2000 mm diameter x 150 mm diameter) with end caps at the base and a removable gas collection cap at the top of each column. These columns represent the physical dimensions of effluent columns found in typical agricultural dairy effluent ponds. There were five treatments: (i) untreated agricultural dairy effluent ("control"), (ii) effluent treated with PFS at 250 mg Fe / L, (iii) effluent treated with 50 mg Fe / L + sulfuric acid at a 50:50 volume ratio; (iv) effluent treated with PFS at 75 mg Fe / L + sulfuric acid at a 50:50 volume ratio; and (v) effluent treated with PFS at 75 mg Fe / L + sulfuric acid at a 55:45 volume ratio; and three duplicate columns for each treatment. Agricultural dairy effluent was collected from the Lincoln University dairy farm and treated according to Table 1 below.

[0097] [Table 1]

[0098] Agricultural dairy effluent was collected from the Lincorn University dairy farm, and 36 liters of this effluent were added to each PVC column. The effluent in each column was mixed using a mechanical mixer, and PFS and sulfuric acid were added to the effluent according to the treatments listed in the table above.

[0099] Gas sampling was performed using the standard procedure for gas sampling (Di et al. 2007). A gas cap was attached to each column, and three gas samples were taken at 30-minute intervals between each sampling (i.e., time=0 min, time=30 min, time=60 min). The gas cap was then removed until the next gas sampling opportunity. Gas sampling was performed at least once a week.

[0100] The concentration of CP gas in each sample was determined using a gas chromatograph (GC) (Model 86C, SRI Instruments, CA, USA) with an automated Gilson GX-271 autosampler (Gilson Inc. M1, USA) coupled to a flame ionization detector (FID). The GC used three HayeSep D-packed pre-columns and two HayeSep D analytical columns. The carrier gases were F and air, and the detector temperature setting was 370°C. Hourly GHG emissions were calculated based on the temperature-corrected rate of increase in GHG concentration in the chamber and the ratio of surface area to headspace volume (Richards et al. 2014). The gas emission rate was calculated using the slope of the change in headspace gas concentration from the samples collected at each sampling opportunity (Hutchinson & Mosier 1981), and this data was used to calculate the methane emission flux (i.e., gas emission rate per unit area). Cumulative emissions were calculated by integrating the measured daily flux over the entire experimental measurement period.

[0101] The oxidation-reduction potential and pH of the liquid in each column were measured immediately after gas sample collection. Oxidation-reduction potential and pH values ​​were measured using a Thermo Fisher Scientific pH 6+ pH / ORP meter (01X 245026W), a 1m BNC connector cable (ECFC 7960205B) supplied by Thermo Fisher Scientific NZ Limited, and a 12x90mm double-junction gel-filled ORP electrode plastic body. More information on this ORP meter can be found at the following link. https: / / www.thermophilus.com / order / catalog / product / ECFC7960205B

[0102] Experiment #2 The objective of Experiment #2 was to determine the effectiveness of effluent treatment against concentrated sulfuric acid (SA) alone, PFS alone, concentrated SA, and PFS versus concentrated SA + ferric sulfate (FS) versus a mixture of hydrogen sulfide and methane emissions.

[0103] Using the same 35L PVC pipe (2.0m depth x 0.15m diameter) as used in Experiment #1, the column was mounted vertically in the tank to minimize temperature fluctuations and simulate typical conditions in a 2m deep discharge pond.

[0104] Methane gas concentration was measured at 30-minute intervals between each sample (i.e., time = 0 min, time = 30 min, time = 60 min). The gas cover was then removed until the next gas measurement opportunity. Gas measurements were performed at least once a week.

[0105] The methane gas concentration was measured using gas chromatography (as explained in Experiment #1 above).

[0106] Hydrogen sulfide gas concentrations were measured after 60 minutes in the enclosure using a Honeywell BW Max XT II Gas Detector (https: / / sps.honeywell.com / usy / en / product / safety / gauty / gas-and-flame-dentationary / potaboles / honeywell-bw-max-xt-ll#overview).

[0107] These processes consisted of the following: FDE = Untreated Farm Milk Runoff Effluent processed by PFS at a rate of 225 mg Fe / L FDE (1.4 ml / L FDE) Effluent treated with concentrated sulfuric acid (SA) alone at SA=0.42 ml / L FDE PFS / SA 67.5 = Effluent treated with PFS using 67.5 mg of Fe / L FDE (0.4 ml / L) + 0.38 ml / L of concentrated sulfuric acid SA FS / SA 67.5 = Evaporate treated with ferric sulfate (FS) was treated with 67.5 mg Fe / L (0.5 ml / L) + 0.42 ml / L concentrated sulfuric acid.

[0108] The results in Figures 4, 5, and 6 clearly demonstrate that PFS / FS + sulfuric acid treatment can simultaneously reduce methane and hydrogen sulfide emissions compared to SA treatment alone.

[0109] Figure 4 shows that the peak hydrogen sulfide gas concentration released for SA treatment alone (41 ppm) is eight times the permissible Time Weighted Average (TWA) concentration for an 8-hour working-day exposure to this gas (5 ppm), while the hydrogen sulfide concentration remains below the critical 5 ppm level for all other treatments, including PFS / FS treatment, along with the SA treatment.

[0110] Furthermore, Figure 6 shows that treatment with SA+PFS and SA+FS results in the maximum reduction in methane emissions (99%) compared to SA alone (96%) or PFS alone (61%).

[0111] Experiment #3 The objective of Experiment #3 was to determine the strength of the dose-response relationship between the rate of SA+PFS treatment and the methane emission flux.

[0112] Experiment #3 was an in vitro experiment conducted using 1 L glass jars with removable lids that allowed for gas capture and analysis over a 40-day period.

[0113] The ratio of added SA to PFS was 33:66, and there were seven rates of Fe / L FDE: 0, 25, 50, 75, 100, 125, and 150 mg. The gas sampling and gas analysis methods were the same as those described in Experiment #1 above.

[0114] The results are shown in Figure 7, and as the curve flattens, methane emissions decrease exponentially as the amount of Fe per liter increases to approximately 100 mg Fe / L.

[0115] Experiment #4 The objective of Experiment #4 was to determine the effectiveness of treating the effluent with different ratios of PFS + concentrated sulfuric acid to reduce methane emissions from FDE.

[0116] This experiment was conducted using IBC Macroco SMS at the Lincoln University Research dairy farm. Each IBC container held 1000L at a depth of 1m, simulating a shallow spill lagoon or pond.

[0117] Each IBC was filled with approximately 950 liters of FDE.

[0118] Two treatments were present: (i) untreated FDE (labeled FDE in Figures 8 and 9), (ii) effluent treated with PFS + sulfuric acid (labeled TE in Figures 8 and 9), and three replicas of each treatment.

[0119] The treatment involved adding 0.3 ml of 96% H2SO4 / L FDE + 0.75 ml of PFS / L FDE (c. 150 mg Fe / L) (SA to PFS solution ratio: 29:71).

[0120] After processing, each IBC was stirred for 2 minutes using an electric mixer (including the untreated FDE).

[0121] Methane gas concentration was measured using the "SETS 5000" adjustable diode laser absorption spectroscopy (TDL-AS) instrument from Geotech QED Environment Systems Ltd.

[0122] As shown in Figure 8, the treated effluent (TE) had a significantly reduced methane emission flux compared to the untreated FDE over a 53-day measurement period.

[0123] As shown in Figure 9, treated effluent (TE) treated with a SA to PFS ratio of 29:71 resulted in a 90% reduction in the total amount of methane released.

[0124] Experiment #5 The objective of Experiment #5 was to determine the effectiveness of "impact treatment" of pond sludge to reduce methane emissions from "sludge" + untreated FDE added to the "sludge". This experiment is important because animal runoff ponds (and tanks) contain "sludge" at the bottom of the ponds (tanks) that receive fresh agricultural dairy runoff daily, and "sludge" as well as FDE can release methane.

[0125] In reality, due to the highly anaerobic conditions at the bottom of the pond / tank, there is likely to be a much larger population of methane-producing substances inhabiting the "sludge" compared to the relatively small population of methanogenic bacteria in the fresh effluent added to the pond / tank. Therefore, using PFS / FS+SA to deactivate methane-producing substances in the "sludge" can be a very effective way to reduce methane emissions from the effluent pond / tank.

[0126] This experiment was conducted using IBC Macroco SMS at the Lincoln University Research dairy farm. Each IBC container held 1000L to a depth of 1m, simulating a shallow spill lagoon or pond. Each IBC was filled with approximately 200L of "sludge" collected from the bottom of the spill pond.

[0127] Two treatments: (i) Untreated "sludge" and untreated FDE were added twice a week (labeled SL UFDE in Figure 10), and (ii) "sludge" treated with PFS + sulfuric acid, and untreated FDE added twice a week (labeled SL TFDE), and three replicas of each treatment.

[0128] The processing rates for the tested and labeled SL TFDE and labeled concentrated SA+PFS / FS combinations were 0.468 ml / L sludge for each processing additive.

[0129] The results from this experiment show that when only the sludge was treated (and when the fresh input of FDE was not treated), methane emissions were reduced by 97% (Figures 10 and 11). This is an important finding for reducing methane emissions in animal runoff treatment, as the data indicates that by simply treating the “sludge” remaining in the drainage pond (i.e., after the majority of the liquid runoff has been pumped out), it is not necessary to treat the fresh runoff entering the pond.

[0130] This new discovery opens up the opportunity to use service tanker-type vehicles as one option for delivering treatment agents directly to ponds, thus eliminating the need for expensive tanks, pumps, mixing equipment, and electronic controls installed on farms to treat fresh effluent each day.

[0131] The cost savings would correspond to a reduction in capital expenditures (Capeex) at each farm, falling from c. $60,000 to less than c. $10,000 (i.e., an 80% reduction in Capex). Figure 10 shows that methane emissions from the treated sludge SL TFDE remained largely zero or near zero over the 90-day trial period. This long-term effectiveness means that service trucks would only need to visit and treat the runoff pond / tank substantially once every 1-3 months (rather than having to treat fresh runoff entering the pond / tank daily).

[0132] Processing and mixing device In relation to Figure 12, a processing and mixing apparatus (TMA) 1 according to a further aspect of the present invention is shown.

[0133] TMA 1 has a first pump 2 that is connected to and can be connected to a conduit 3 via fluid communication, or is adapted to be able to communicate with a discharge pond (not shown).

[0134] TMA 1 also has a supply source for SA 4 and the second pump 5, along with a supply source for PFS or FS 6 and the third pump 7.

[0135] The supply sources for SA 4 and its associated pump 5, as well as the supply sources for PFS or FS 6 and its associated pump 7, are connected to conduits 8 and 9, respectively, which connect to the mixing chamber / manifold 10.

[0136] The mixing chamber / manifold 10 (hereinafter referred to as manifold for ease of reference) has an inlet port 11 at one end connected to the pump 2 via conduit 12, which can be used to deliver the effluent to the manifold.

[0137] Optionally, the manifold 10 has a number of vanes 13 arranged therein, which, when in use, create turbulence in the fluid flow of the liquid effluent to produce a mixture. The manifold 10 has an outlet port 14 at the end opposite the inlet 11, and the outlet port 14 is adapted to be releasably connected to a conduit 15 to which the treated effluent can be returned to a pond.

[0138] TMA 1 also has an ORP sensor 16 positioned close to the inlet port 11 to measure the oxidation-reduction potential of the inflow and outflow. The ORP sensor 16 and pumps 2, 5, and 7 are all controlled by a properly programmed PLC 18, and a pH sensor 17 is also positioned close to the inlet port 11 to measure the acidity of the inflowing effluent.

[0139] Preferably, the manifold may be adapted to allow for quick mating / unmating of sensors, so that the sensors can be cleaned and recalibrated before each process.

[0140] The PLC initiates the processing process by turning on pumps 2, 5, and 7, and is programmed to turn off pumps 2, 5, and 7 when Eh = +100mV or until the pH reaches 4.

[0141] In relation to Figure 13, a mixing device 1 is provided, which is positioned on a stretcher trolley 130 and has elements similar to those in Figure 12, given as reference numbers. The mixing device 1 has a PLC 18 connected to an ORP sensor 16 and a pH sensor 17, along with pumps 2, 5, and 7.

[0142] Track 131 is connected to flexible conduits 3, 5 which are in fluid communication with the outflow pond 140, and preferably the pond 140 has a conventional mixer 141 used in the outflow pond to assist in mixing the combined treatment with the liquid outflow.

[0143] As previously stated herein, the use of PFS / FS + sulfuric acid (H₂SO₄) as a double treatment has been found to simultaneously reduce emissions of the potent greenhouse gas methane and the toxic gas hydrogen sulfide (Figures 13a, b). However, simply combining (i.e., mixing) PFS / FS solution with concentrated sulfuric acid is impossible due to the fact that it produces a “paste / solid” that cannot be pumped.

[0144] In relation to Figure 14, it can be seen that the concentrated SA and PFS 50:50 mixture is an opaque, milky white paste / solid.

[0145] To overcome this limitation, the inventors conducted a series of laboratory tests and found a method for combining the PFS solution with sulfuric acid, so that the mixture remains as a pressurized liquid (and therefore can be used as a single-step additive to treat animal effluent and reduce methane emissions).

[0146] The inventors diluted concentrated sulfuric acid by gradually adding it to water in a laboratory beaker that had been sieved in an ice bath. This ice bath was used due to the exothermic reaction that occurs when concentrated sulfuric acid is added to water. Once cooled, each batch of dilute sulfuric acid was then gradually mixed into a beaker containing ferric sulfate. As shown in Figure 14, the physical state of the mixture (i.e., liquid or solid) was observed and photographed, and it was evident from the observations when the mixture was liquid or solid. This laboratory work was carried out in a laboratory fume cabinet with the hood down to ensure that there was no risk of injury to the staff performing the experiment.

[0147] In contrast, Figure 15 shows that the diluted (33%) SA and PFS 50:50 mixture produces a translucent reddish-brown liquid that is not viscous (i.e., has a viscosity similar to water) and is injectable / pumpable.

[0148] The inventors discovered that the PFS solution can be combined with a more dilute (33%) solution of sulfuric acid, and that the mixture remains in liquid form for nine months, the age of the mixture shown in the photograph in Figure 15.

[0149] The inventors have developed a dose-response curve showing that using a diluted SA / PFS mixture increases the treatment rate of agricultural dairy product runoff relative to methane gas emissions (Figure 16).

[0150] Further detailed explanation including preferred or alternatives Embodiments of the present invention The present invention includes cattle, particularly dairy cows, but also includes applications to other agriculturally raised animals (e.g., milk cows, pigs, sheep).

[0151] Therefore, it should be understood that the present invention can also be broadly applied in relation to other farmland-based animals where liquid spills need to be grouped into areas where they should be collected and stored or placed.

[0152] This invention relates to the surprising discovery of adding both ferric sulfate and concentrated sulfuric acid to liquid animal effluents, in contrast to the startk contrast, which aims to reduce the ionic sulfur content in the effluent to prevent hydrogen sulfide generation (HulshoPol et al. 1998, Metals and Eddy, 2014), and can significantly and simultaneously reduce methane and hydrogen sulfide emissions.

[0153] However, it is also important to note that (human) wastewater treatment engineering literature actually suggests that sulfuric acid can cause “failure” of anaerobic processes for organic digestion used in many wastewater treatment facilities (HulshoPol et al. 1998, Metals and Eddy, 2014). Therefore, it was quite unexpected that the addition of ferric sulfate and sulfuric acid (given the above concerns) would be useful in reducing methane and / or hydrogen sulfide emissions from animal effluents.

[0154] The main reason wastewater treatment plant engineers do not want large amounts of sulfate in anaerobic treatment plants is that it inhibits the complete anaerobic destruction of organic matter in wastewater.

[0155] In contrast, the present invention preferably uses ferric sulfate (or ferric sulfate) + sulfuric acid to increase the aerobic state (i.e., oxidation-reduction potential) of the effluent and thus prevent complete anaerobic destruction of organic matter in order to reduce the generation and release of methane gas.

[0156] As a preferred disposal method for treated human wastewater discharge, it is important to maintain low sulfuric acid levels in the anaerobic treatment of human wastewater (e.g., Christchurch City Council, 2019; Brittania, 2019) (e.g., Christchurch City Council, 2019; Brittania Ia, 2019). When treated wastewater discharge eventually enters rivers, lakes, or oceans, any organic matter remaining in the wastewater will (biochemically) deplete the rivers, lakes, or oceans of oxygen.

[0157] The oxygen demand (BOD) of organic materials causes fish death and other aquatic organism death (MFE, 207b). The BOD of treated effluent must be kept low to avoid adverse effects on the receiving water (MFE 207b), and therefore, anaerobic processes must be inhibited by the presence of sulfates.

[0158] Therefore, wastewater treatment plants do not want to add ferric sulfate or sulfides containing ferric sulfate to wastewater.

[0159] HulshoffPol et al. (1998) specifically demonstrate that the presence of sulfuric acid can cause serious problems when anaerobically treating sulfates containing organic wastewater. This is of particular importance because the concentration of free hydrogen sulfide (FS) can cause failure of wastewater treatment processes due to sulfidation toxicity.

[0160] According to Hulshoff Pol et al. (1998), gaseous and dissolved sulfides pose physical and chemical (corrosive, malodorous, and chemically-driven oxygen requirements) or biological (toxic) constraints that can lead to process failures.

[0161] Therefore, attempts have been made to eliminate or mitigate the effects of sulfates in wastewater treatment plants. For example, strategies currently available to do this include i) removal of organic matter, ii) removal of sulfates, or iii) removal of both (Hulshof Pol et OZ. 1998).

[0162] Zub et al. (2008) also provided a list of strategies for removing sulfur-containing compounds from wastewater before treatment to ensure that they do not adversely affect the biological processes of wastewater treatment.

[0163] Treated animal runoff is generally applied on land, and treating animal runoff with ferric sulfate along with agricultural sulfuric acid is different from treating wastewater; here, as mentioned above, the risk of impact in terms of biochemical oxygen demand (BOD) is far lower compared to human runoff discharged into surface water.

[0164] Therefore, the present invention provides an unforeseen opportunity to suppress the anaerobic destructive process in animal runoff before methane gas is generated, whereas human wastewater engineers cannot interfere with the anaerobic process by adding ferric sulfate alone, which adds sulfate-containing compounds rather than removing them.

[0165] Furthermore, adding both PFS or FS to SA simultaneously reduces the risk of releasing toxic hydrogen sulfide gases compared to adding SA alone. This is because the iron in PFS / FS reacts with the sulfides produced from SA to form iron sulfide precipitates instead of the hydrogen sulfide gas that would otherwise be produced.

[0166] The present invention also offers the opportunity to return more carbon to the soil by inhibiting anaerobic processes before methane is produced (i.e., instead of losing carbon to the atmosphere as methane, which causes greenhouse gas emissions). Treated effluent / sludge can be applied to land because it contains organic matter that has a large amount of readily available carbon (in the form of simple organic compounds such as acetic acid) in it. The reason is that if carbon can be recycled back into the atmosphere, then it can be recycled back into the atmosphere.

[0167] In a preferred embodiment, the oxidation-reduction potential of the effluent / sludge may be a method used to evaluate an appropriate dose or to test whether the treatment is effective.

[0168] Polyferric sulfate or combinations of ferric sulfate and ferric sulfate may be added to liquid animal spills either during transport to the spill storage area or once delivered, but are not limited to the following. pond Lagoon sauce; tank Storage or transport containers Other storage facilities or storage devices

[0169] The spillage storage area may include a mixed configuration to completely distribute the combined treatment throughout the liquid spillage within it.

[0170] Alternatively, the spill storage area may be treated by an external mixing device that can maintain permanent or temporary fluid communication with the liquid spill within the spill storage area.

[0171] The present invention demonstrates the remarkable result that treating the “sludge” at least partially at the bottom of an empty pond is highly effective in reducing methane emissions from both the “sludge” and any remaining liquid spillage, and is highly effective in reducing methane emissions from any fresh liquid spillage subsequently added to the pond or other storage area.

[0172] This reduces the Capex required to reduce methane and hydrogen sulfide emissions from drainage ponds by eliminating the need for expensive equipment installed on farms.

[0173] For example, the treatment agents may be delivered directly to the outflow pond from a vehicle having a tank for each treatment agent (as conceptually shown, for example, in Figure 13). Alternatively, a very simple mixing configuration can be set up using a few pumps and tanks for each treatment agent (as conceptually shown, for example, in Figure 12).

[0174] Sources of liquid animal spillage can generally be cattle yards or milking sheds / parabars for dairy cows.

[0175] However, the sources of liquid animal spills should not be limited and may include one or more of the following: Stock Lane (or Stock Race) Stock supply pads Stock containment facility Livestock transport vehicle Track as described in the claims Spillage treatment tanks (e.g., sheep / cattle trucks) Animal holding pen or yard

[0176] In some preferred embodiments, the amount of dose for initially treating the liquid animal effluent and / or sludge may be a standard amount based on the volume of liquid animal effluent and / or sludge being treated.

[0177] In another preferred embodiment, the amount of dose for initially treating liquid animal effluent and / or sludge can be based on achieving a specific redox potential reading (>0mV) after treatment. Since this treatment would be successful if the redox potential increases above 0mV, this indicates that aerobic conditions are being generated by the treatment, and therefore obligate anaerobic methanogenic populations are unable to survive or produce methane.

[0178] In practice, the oxidation-reduction potential is not adjusted to substantially above 100mV for the primary purpose of maintaining pH, so it is not acidic enough to cause corrosion of the pumps used to guide the effluent into the manifold / chamber, or corrosion of other effluent management equipment on the farm.

[0179] All disclosures of all applications, patents and publications cited above and below are incorporated herein by reference, if any.

[0180] Any reference to prior art in this specification should not be construed as an affirmative response or any form of proposal in which the prior art forms part of the common general knowledge in the field of endeabour in any country in the world.

[0181] This technology can also be said to extend to any or all combinations of two or more of these parts, elements, or features, individually or collectively, to the parts, elements, and features referenced or indicated in the application specifications.

[0182] Wherever an integer or component having known equivalents is referred to in the preceding description, those integers are incorporated herein as to be described separately.

[0183] It should be noted that various changes and modifications to the currently preferred embodiments described herein will be obvious to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the Art and without diminishing its associated advantages. Therefore, such changes and modifications are intended to be included within the Art.

Claims

1. below: - Ferric polysulfate (PFS) or ferric sulfate (FS); and - Sulfuric acid (SA) The combined use of liquid animal runoff and / or sludge (i.e., combined treatment) to reduce methane emissions from liquid animal runoff and / or sludge (i.e., combined treatment) compared to untreated liquid animal runoff and / or sludge.

2. The use of SA and PFS / FS according to claim 1, wherein the dose rate is calculated from the measurement of the redox potential of the liquid animal effluent and / or sludge.

3. The use of SA and PFS / FS according to claim 1, wherein the combined treatment is added to the stored liquid animal spillage after about 50% or more of the liquid animal spillage has been removed from where the liquid animal spillage is held, to reduce the amount of ferric sulfate (PFS) or ferric sulfate (FS), and the sulfuric acid (SA) necessary for the first treatment of the spillage and / or sludge is added to the stored liquid animal spillage.

4. The use of the combination treatment according to claim 1, wherein the combination treatment is used to increase the oxidation-reduction potential of the liquid animal effluent and / or sludge.

5. The use of the combination treatment according to claim 3, characterized by raising the oxidation-reduction potential to more than 0 mV.

6. The use of the combination treatment according to claim 3, characterized by raising the oxidation-reduction potential to 100 mV.

7. The use of the combined treatment according to any one of claims 1 to 3, wherein the liquid animal effluent and / or sludge is retained as follows: - Pond - sauce, - Lagoon - Tank or - A container for storage or transport.

8. Use of the combined processing according to any one of claims 1 to 3, wherein the PFS or FS and SA are as follows: The liquid animal spills and / or sludge are added sequentially or simultaneously, separately, or separately to the liquid animal spills and / or sludge. They are mixed together immediately before adding the LAE and / or sludge.

9. A combined treatment for reducing methane emissions from liquid animal runoff and / or sludge compared to untreated liquid animal runoff and / or sludge, the following: Sulfuric acid (SA) component Ferric sulfate (PFS) or ferric sulfate (FS) component Combination processing, including

10. The combination treatment according to any one of claims 1 to 6 or 9, wherein the ratio of the SA component to the PFS component or FS component is substantially in the range of 29:71-50:

50.

11. The combination treatment for reducing methane emissions from liquid animal spills according to claim 4, wherein the concentration of the PFS or FS is substantially in the range of 50 mg Fe / L to 100 mg Fe / L.

12. A method for reducing methane emissions from liquid animal runoff, comprising the step of raising the oxidation-reduction potential of the liquid animal runoff and / or sludge from -200mV or less to a pond greater than 0mV.

13. A method for reducing methane emissions according to claim 11, wherein the oxidation-reduction potential rises to more than 100 mV.

14. The method according to claim 12 or 13, wherein the reduction in methane emissions is at least substantially 90% compared to untreated liquid animal spills.

15. A method for reducing methane emissions, comprising the step of adding both of the following to liquid animal spills and / or sludge: - Sulfuric acid (SA) - Ferric sulfate (PFS) or ferric sulfate (SA).

16. The method according to claim 12 or the use according to claim 8, wherein the percentage ratio of SA to PFS / FS in the mixture is substantially between 29% SA and 50% SA.

17. The method according to claim 12 or the use according to claim 8, wherein the percentage ratio of SA to PFS / FS in the mixture is substantially 50%SA to 50%SA.

18. a) Ferric sulfate (PFS) or ferric sulfate (FS) b) Concentrated sulfuric acid (SA) Compared to untreated liquid animal runoff and / or sludge, methane emissions and H from liquid animal runoff and / or sludge are compared to those from untreated liquid animal runoff and / or sludge. 2 For simultaneous reduction of S, it is used to treat liquid animal spills and / or sludge.

19. A method for reducing methane and hydrogen sulfide emissions from liquid animal runoff and / or sludge, comprising simultaneously administering the following: - Concentrated sulfuric acid (SA); and - Ferric sulfate (FS) or polyferric sulfate (PFS)

20. To reduce methane and / or hydrogen sulfide emissions from untreated liquid animal runoff and / or sludge, the transformation of liquid animal runoff and / or sludge from anaerobic to aerobic conditions reduces methane and / or hydrogen sulfide emissions from untreated liquid animal runoff and / or sludge by creating an aerobic environment that is hostile to methane-producing substances residing on or within the sludge in runoff ponds or other runoff repositories.

21. Use of the following combination treatments to increase the redox potential of liquid animal effluents and / or sludge: - Polyferric sulfate (PFS) or ferric sulfate (FS); and - Sulfuric acid (SA).

22. The use of sulfuric acid and PFS / FS according to claim 1, which increases the oxidation-reduction potential while minimizing the acidification level of effluent and / or sludge so that the pH remains substantially above 4.

23. The use of the sulfuric acid (SA) and PFS / FS combination according to claim 21, wherein the oxidation-reduction potential rises to above 0 mV.

24. Use of a combination of concentrated sulfuric acid (SA) and polyferric sulfate (PFS) or ferric sulfate (FS) for treating liquid animal effluent, wherein the dose of the SA+PFS or FS combination is substantially 0.468 ml / L of liquid animal effluent and / or sludge, and the amount delivered is required to achieve a redox potential greater than 0 mV.

25. A method for reducing methane emissions from stored liquid animal effluent and / or sludge compared to untreated liquid animal effluent or untreated sludge, comprising the following steps: a) a step of determining whether PFS or FS to be added to the effluent together with SA to form a treatment; b) a step of adding and mixing an effective amount of the treatment from step a) to liquid animal effluent or sludge to increase the redox potential of the liquid animal effluent / sludge above 0 mV.

26. When treating liquid animal effluent or sludge using a combination of PFS / FS and SA treatment to reduce methane emissions from untreated effluent or untreated sludge, use of oxidation-reduction potential to determine: - A quantity for the initial treatment of liquid animal spills or sludge, and / or - Is the initial processing dose effective?

27. A method for treating sludge associated with liquid animal spills, comprising the following steps: a) Treat the liquid animal effluent to substantially increase its oxidation-reduction potential from below 200 mV to above 0 mV.

28. Processing and mixing apparatus including the following: a) A first pump that is fluid-connectable to a conduit and is connected to or adapted to be in a fluid-connected state, and a first pump adapted to be connectable to an outflow pond or tank, b) SA source and second pump, c) Ferric sulfate (PFS) or ferric sulfate (FS) source and a third pump, d) Mixing chamber / manifold including a mixing chamber / manifold, It comprises an inlet connected to the pump to deliver discharge to the chamber / manifold, and an outlet port, the outlet port being connected to the outlet port, A processing and mixing apparatus wherein a source of SA and a source of PFS / FS, which are in fluid communication with the mixing chamber / manifold, are capable of supplying SA and PFS to the chamber / manifold, respectively, and the mixing chamber / manifold is adapted to be connectable to a conduit that can return the processed effluent to the pond.

29. Use of SA and PFS / FS according to claim 1 to reduce methane emissions compared to untreated sludge and / or untreated liquid animal effluent: From sludge, and / or, From the liquid animal runoff, including any further untreated liquid animal runoff that enters the pond over a period of at least one month.

30. Compositions including the following: Liquid animal spills and / or sludge Sulfuric acid and PFS / FS.

31. The composition according to claim 30, wherein the composition has a pH of substantially 4.

32. The composition according to claim 31, wherein the oxidation-reduction potential of the composition is substantially 0 mV or higher.

33. A composition substantially as described above, wherein the oxidation-reduction potential of the composition is substantially from 0 mV to substantially 100 mV.

34. Compositions including the following: Liquid animal spills and / or sludge Sulfuric acid and PFS / FS The oxidation-reduction potential of the composition is substantially between 0 mV and substantially 100 mV.

35. The use, method, or combined treatment according to any one of claims 1 to 34, wherein the redox potential of the composition is shifted from substantially -200 mV to substantially 0 mV, up to a maximum of substantially 100 mV.

36. Treatment composition containing the following mixture: Dilute sulfuric acid (SA) Ferric sulfate (PFS) / Ferric sulfate (FS).

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