Improvement of ammonium sulfate production process by recycle portion of ammonium sulfate to the separation unit

Abstract

Disclosed are improved methods and systems for producing ammonium sulfate and calcium carbonate by capturing carbon dioxide and utilizing calcium sulfate. Additional ammonium sulfate may be added to a combination of ammonium sulfate and calcium carbonate before separation of at least a portion of the ammonium sulfate. The additional ammonium sulfate may be in some instances at least a portion of the separated ammonium sulfate.

Description

DESCRIPTIONIMPROVEMENT OF AMMONIUM SULFATE PRODUCTION PROCESS BY RECYCLE PORTION OF AMMONIUM SULFATE TO THE SEPARATION UNITCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to and the benefit of Indian Application No. 202441085302, filed November 7, 2024, the contents of which is incorporated into the present application by reference in its entirety.BACKGROUND OF THE INVENTIONI. Field of the Disclosure

[0002] This disclosure generally concerns improved methods for the production of ammonium sulfate and calcium carbonate utilizing carbon dioxide and gypsum.II. Background

[0003] Over the past decade, the world has become more conscious of the adverse effects on the environment posed by disposing industrial processing wastes such as waste gypsums like phosphogypsum (PG) or red gypsum (RG). Waste gypsums have been disposed by stacking on land or discharge to the sea. However, both methods of disposal have possible adverse environmental effects.

[0004] Further, reduction of CO2 emission is presently among the top priorities of many industries. Chemical utilization of CO2 through its reduction to CO and involvement of chemical reactions requires excessive consumption of energy. That is one of the reasons why, presently, many chemical companies have made significant efforts to reduce CO2 emission by storing CO2 in underground deep storage.

[0005] There is a need for additional ways to reduce CO2 as well as reduce waste gypsums.

[0006] One such way is to use CO2 and waste gypsums to produce ammonium sulfate. Production of ammonium sulfate in industry is expensive. One process comprises reaction of ammonia with expensive and corrosive concentrated sulfuric acid. The reaction is also performed under severe reaction conditions. Another process comprises melting salts of sulfate and300332254.1 - 1 -ammonium nitrate to produce a double salt of ammonium sulfate nitrate. This method is also expensive, energy-intensive, and involves a multistep process. In view of this, production of ammonium sulfate from calcium sulfate and CO2 has become a widely studied process.SUMMARY OF THE INVENTION

[0007] A solution to at least some of the problems discussed above, including an efficient utilization of industrial by-products such as a gypsum and carbon dioxide have been discovered. In one aspect, the conversion of CaSO4 through a reaction with CO2 and ammonia is used to produce ammonium sulfate. In some instances, calcium carbonate is also produced in such reactions. Herein, significant improvements to the process conditions and product composition has been found by adding additional ammonium sulfate to the separation unit used to separate the ammonium sulfate from a mixture of calcium carbonate and ammonium sulfate. Separation of the ammonium sulfate is improved, separation of the solids and the liquids in the mixture of calcium carbonate and ammonium sulfate are improved, and a reduction of separation time is realized. Further, the stoichiometric ratio of the main product, such as calcium carbonate / ammonium sulfate can be modified by adding the additional amount of ammonium sulfate and / or by recycling at least a portion of the separated ammonium sulfate to the separation unit. In some instances, the separation of calcium carbonate from ammonium sulfate is carried out by filtration and the additional ammonium sulfate is added to the filter or components contacting the filter.

[0008] In some aspects, the solution resides in reacting calcium sulfate (CaSCM), carbon dioxide (CO2), and a source of ammonia, such as one or both of ammonia (NH3) and ammonium hydroxide (NH4OH), to produce a first product comprising ammonium sulfate ((NH4)2SO4), and calcium carbonate (CaCCh). This reaction can be performed in one reaction vessel or these reactions that occur can be divided. Non-limiting example reaction (1) is shown below. The compositions, systems, and method herein provide the benefit of utilizing both carbon dioxide, including from industrial exhaust sources, and gypsum, including from by-product and recycled sources. This can result in decreasing carbon dioxide released into the atmosphere while producing useful products. The carbon dioxide and gypsum utilization may concern the generation of a first product, such as calcium carbonate (CaCCh) and ammonium sulfate ((NH4)2SO4). When other sources of ammonia is used, different or additional products can be produced.(1) CaSO4+ CO2 + 2NH3+ H2O CaCO3J, + (NH4)2SO4300332254.1 - 2 -

[0009] Certain aspects concern a final product that contains a mixture comprising, consisting essentially of, or consisting of any of the above chemicals or a combination thereof. Embodiments of the disclosure are improvements to known methods of generating calcium carbonate (CaCCE) and ammonium sulfate ((NH4)2SO4 fertilizers, including fertilizer comprising, consisting essentially of, or consisting of ammonium sulfate (NH4)2SO4, including by involving the use of CO2 and / or gypsum, such as phosphogypsum.

[0010] Certain embodiments provide utilization (such as by recycling) of ammonium sulfate (NFU SCh for synthesis of a second product, such as a product containing both ammonium sulfate (NFU SCh and calcium carbonate (CaCCh) but with an ammonium sulfate to calcium carbonate ratio higher than is produced by reacting calcium sulfate (CaSCM), carbon dioxide (CO2), and a source of ammonia. In some instances, the molar ratio of ammonium sulfate to calcium carbonate in the second product is >1: 1, such as a molar ratio of 1.1: 1 to 6:1, such as at, greater than, less than, or between 1.1: 1, 1.2: 1, 1.3: 1, 1.4: 1, 1.5:1, 1.6: 1, 1.7: 1, 1.8: 1, 1.9: 1, 2:1, 2.1: 1, 2.2: 1, 2.3:1, 2.4: 1, 2.5: 1, 2.6: 1, 2.7: 1, 2.8: 1, 2.9:1, 3:1, 3.1: 1, 3.2: 1, 3.3:1, 3.4: 1, 3.5:1, 3.6:1, 3.7: 1, 3.8:1, 3.9: 1, 4: 1, 4.1: 1, 4.2:1, 4.3:1, 4.4: 1, 4.5: 1, 4.6: 1, 4.7:1, 4.8: 1, 4.9: 1, 5:1, 5.1:1, 5.2: 1, 5.3: 1, 5.4: 1, 5.5:1, 5.6: 1, 5.7: 1, 5.8: 1, 5.9: 1, and 6: 1, or any range thereof. The product produced may or process of producing the product can be modified to produce multiple products with different ratios of the calcium carbonate to ammonium sulfate.

[0011] Certain aspects are directed to a method of producing ammonium sulfate. In some instances, the method may include any one of or a combination of steps (a), (b), and (c). Step (a) may include contacting calcium sulfate (CaSCM) with carbon dioxide (CO2) and a source of ammonia to generate a first product comprising calcium carbonate (CaCCh) and ammonium sulfate ((NIE SCM). Step (b) may include contacting the first product with additional ammonium sulfate to form an ammonium sulfate-enriched first product having a greater concentration of ammonium sulfate than the first product. Step (c) may include separating at least a portion of the ammonium sulfate from the ammonium sulfate-enriched first product to form a separated ammonium sulfate and a second product. In some instances, the additional ammonium sulfate may include at least a portion of the separated ammonium sulfate.

[0012] In some aspects, the source of CaSCM in step (a) comprises waste gypsum and / or recycled gypsum. In certain aspects, the source of CO2 in step (a) comprises exhaust waste gas from an industrial plant and / or flue gas. In some aspects, the source of CaSCE in step (a) comprises300332254.1 - 3 -phosphogypsum and / or red gypsum. In some aspects, the source of ammonia is a solution of ammonium hydroxide, ammonium, ammonium carbonate, ammonia gas, succinimide, and / or phthalimide.

[0013] In some aspects, the first product may comprise a solution and / or a gel. In some aspects, the additional ammonium sulfate may include solid ammonium sulfate. In some aspects, the solid ammonium sulfate may comprise a powder. In some aspects, the additional ammonium sulfate may include ammonium sulfate in solution. In some aspects, the additional ammonium sulfate may include ammonium sulfate in a solution that contains a higher concentration of ammonium sulfate than the concentration of the ammonium sulfate in the first product. In some aspects, the separating at least a portion of the ammonium sulfate from the ammonium-sulfate enriched first product may include separating by distillation. In some aspects, the separating at least a portion of the ammonium sulfate from the ammonium-sulfate enriched first product may include separating by filtration. In some aspects, the second product may include calcium carbonate and ammonium sulfate. In some aspects of the method, a computer processing unit may control the ratio of the calcium carbonate to the ammonium sulfate in the second product, and the computer processing unit may control the amount of additional ammonium sulfate contacting the first product. In some aspects, the method further may include drying the second product to form a solid second product.

[0014] In some aspects, the second product further comprises calcium sulfate, ammonia, and / or ammonium hydroxide. In some aspects, the contacting calcium sulfate with carbon dioxide and a source of ammonia occurs at approximately 30°C to 65°C, such as at, greater than, less than, or between any one of 30, 35, 40, 45, 50, 55, 60, or 65°C, or any range thereof. In some aspects, the contacting of the first product with additional ammonium sulfate occurs at approximately 30°C to 65°C, such as at, greater than, less than, or between any one of 30, 35, 40, 45, 50, 55, 60, or 65 °C, or any range thereof.

[0015] In some aspects, the contacting calcium sulfate with carbon dioxide and a source of ammonia occurs at approximately 5 to 25 bar, such as at, greater than, less than, or between any one of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 bar, or any range thereof. In some aspects, the contacting of the first product with additional ammonium sulfate occurs at approximately 5 to 25 bar such as at, greater than, less than, or between any one of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 bar, or any range thereof. In300332254.1 - 4 -some aspects, the method may further include contacting the second product with a micronutrient and / or a nitrogen fertilizer other than ammonium sulfate.

[0016] Certain aspects are directed to a system for producing ammonium sulfate. In some aspects, the system contains a reactor capable of receiving calcium sulfate (CaSCM), carbon dioxide (CO2), and a source of ammonia, wherein the reactor is capable of providing conditions to generate a first product comprising calcium carbonate (CaCCh) and ammonium sulfate ((NH4)2SO4). In some aspects, a separator is in fluid communication with the reactor. The separator may be capable of separating at least a portion of the ammonium sulfate from the first product to form a separated ammonium sulfate and a second product. In some aspects, a conduit is in fluid or mechanical communication with the separator. The conduit may be capable of transporting at least a portion of the separated ammonium sulfate to contact the first product between the reactor and the separator or at the separator. In some aspects, the reactor is capable of receiving and reacting carbon dioxide from a flue gas and / or a waste gas from an industrial plant. In some aspects, the carbon dioxide from the flue gas and / or waste gas is not purified to separate or concentrate the carbon dioxide in the flue gas and / or waste gas before reacting the carbon dioxide to form the calcium carbonate.

[0017] Also disclosed are the following Aspects 1 to 15 of the present invention.

[0018] Aspect 1 is a method of producing ammonium sulfate and calcium carbonate, the method comprising the steps of: (a) contacting calcium sulfate (CaSCM) with carbon dioxide (CO2) and a source of ammonia to generate a first product comprising calcium carbonate (CaCCh) and ammonium sulfate ((NH4)2SO4); (b) contacting the first product with additional ammonium sulfate to form an ammonium sulfate-enriched first product having a greater concentration of ammonium sulfate than the first product; and (c) separating at least a portion of the ammonium sulfate from the ammonium sulfate-enriched first product to form a separated ammonium sulfate and a second product, wherein the additional ammonium sulfate comprises at least a portion of the separated ammonium sulfate.

[0019] Aspect 2 is the method of aspect 1 , wherein the first product comprises a solution and / or a gel.

[0020] Aspect 3 is the method of any one of aspects 1 to 2, wherein the additional ammonium sulfate comprises solid ammonium sulfate.300332254.1 - 5 -

[0021] Aspect 4 is the method of aspect 3, wherein the solid ammonium sulfate comprises a powder.

[0022] Aspect 5 is the method of any one of aspects 1 to 4, wherein the separating at least a portion of the ammonium sulfate from the ammonium sulfate-enriched first product comprises separating by distillation.

[0023] Aspect 6 is the method of any one of aspects 1 to 5, wherein the second product comprises calcium carbonate and ammonium sulfate.

[0024] Aspect 7 is the method of aspect 6, wherein a computer processing unit controls a ratio of the calcium carbonate to the ammonium sulfate in the second product, the computer processing unit controlling an amount of additional ammonium sulfate contacting the first product.

[0025] Aspect 8 is the method of any one of aspects 1 to 7, further comprising drying the second product to form a solid second product.

[0026] Aspect 9 is the method of any one of aspects 1 to 8, wherein: the calcium sulfate is a waste gypsum and / or a recycled gypsum, preferably wherein the calcium sulfate is phosphogypsum and / or red gypsum; the source of ammonia is one or both of ammonia (NH3) and ammonium hydroxide (NH4OH); and / or a source of the carbon dioxide comprises waste gas from an industrial plant and / or flue gas.

[0027] Aspect 10 is the method of any one of aspects 1 to 9, wherein the second product further comprises calcium sulfate, ammonia, and / or ammonium hydroxide.

[0028] Aspect 11 is the method of any one of aspects 1 to 10, wherein: the contacting calcium sulfate with carbon dioxide and a source of ammonia occurs at approximately 30°C to 65°C; and / or the contacting the first product with additional ammonium sulfate occurs at approximately 30°C to 65°C.

[0029] Aspect 12 is the method of any one of aspects 1 to 11, wherein: the contacting calcium sulfate with carbon dioxide and a source of ammonia occurs at approximately 5 to 25 bar; and / or the contacting of the first product with additional ammonium sulfate occurs at approximately 5 to 25 bar.

[0030] Aspect 13 is the method of any one of aspects 1 to 12, further comprising contacting the second product with a micronutrients and / or a nitrogen fertilizer other than ammonium sulfate.

[0031] Aspect 14 is a system for producing ammonium sulfate and calcium carbonate, the system comprising: a reactor capable of receiving calcium sulfate (CaSCM), carbon dioxide (CO2),300332254.1 - 6 -and a source of ammonia, wherein the reactor is capable of providing conditions to generate a first product comprising calcium carbonate (CaCCh) and ammonium sulfate ((Nt SCM); a separator in fluid communication with the reactor, the separator capable of separating at least a portion of the ammonium sulfate from the first product to form a separated ammonium sulfate and a second product; and a conduit in fluid communication with the separator, the conduit capable of transporting at least a portion of the separated ammonium sulfate to contact the first product between the reactor and the separator or at the separator.

[0032] Aspect 15 is the system of aspect 14, wherein the reactor is capable of receiving and reacting carbon dioxide from a flue gas and / or a waste gas from an industrial plant, preferably wherein the carbon dioxide from the flue gas and / or waste gas is not purified to separate or concentrate the carbon dioxide in the flue gas and / or waste gas before reacting to form the calcium carbonate.

[0033] The term “fertilizer” is defined as a material applied to soils or to plant tissues to supply one or more plant nutrients essential or beneficial to the growth of plants and / or stimulants or enhancers to increase or enhance plant growth.

[0034] The term “granule” can include a solid material. A granule can have a variety of different shapes, non-limiting examples of which include a spherical, a puck, an oval, a rod, an oblong, or a random shape.

[0035] The term “particle” can include a solid material less than a millimeter in its largest dimension.

[0036] The terms “particulate” or “powder” can include a plurality of particles.

[0037] The terms “about” or “approximately” as used herein are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0038] The terms “wt. %,” “vol.%,” or “mol.%” refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt. % of component.300332254.1 - 7 -

[0039] The use of the word “a” or “an” when used in conjunction with the term “comprising” may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”

[0040] The phrase “and / or” means “and” or “or”. To illustrate, A, B, and / or C includes: A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C. In other words, “and / or” operates as an inclusive or.

[0041] The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0042] The compositions and methods for their use can “comprise,” “consist essentially of,” or “consist of’ any of the ingredients or steps disclosed throughout the specification. Compositions and methods “consisting essentially of’ any of the ingredients or steps disclosed limits the scope of the claim to the specified materials or steps which do not materially affect the basic and novel characteristic of the claimed invention.

[0043] It is contemplated that any embodiment discussed in this specification can be implemented with respect to any method or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention.

[0044] Other objects, features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating specific embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.BRIEF DESCRIPTION OF THE DRAWINGS

[0045] The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein.300332254.1 - 8 -

[0046] The Figure: a schematic of a system and method for producing ammonium sulfate and calcium carbonate according to a non-limiting example of a system and method disclosed herein.DETAILED DESCRIPTION OF THE INVENTION

[0047] Certain aspects of the present disclosure provide benefits over existing ammonium sulfate and calcium carbonate production processes by utilizing carbon dioxide capture techniques, including by an efficient utilization of gypsum, such as a waste gypsum. In one aspect, the conversion of CaSO4 through a reaction with CO2 and a source of ammonia to form calcium carbonate and ammonium sulfate first product includes adding additional ammonium sulfate to a separation unit for separating ammonium sulfate from the first product. In some instances, adding the additional ammonium sulfate leads to significant improvement of process conditions and product composition such as improving separation of the ammonium sulfate, improving separation of solids from a solid / liquid mixture, and / or reduction of the time required for separation of the ammonium sulfate.

[0048] In some instances, the stoichiometric ratio of the ammonium sulfate to the calcium carbonate after separation of a portion of the ammonium sulfate can be increased by adding the additional ammonium sulfate to the separation unit. In some aspects, the additional ammonium sulfate is all or a portion of the separated ammonium sulfate. In some instances, the separation of calcium carbonate from ammonium sulfate is carried out by filtration, distillation, or filtration and distillation. In some instances, the molar ratio of ammonium sulfate to calcium carbonate in the second product is >1: 1, such as a molar ratio of 1.1: 1 to 6: 1, such as at, greater than, less than, or between 1.1:1, 1.2: 1, 1.3: 1, 1.4: 1, 1.5:1, 1.6: 1, 1.7: 1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2: 1, 2.3: 1, 2.4:1, 2.5: 1, 2.6: 1, 2.7: 1, 2.8: 1, 2.9:1, 3: 1, 3.1: 1, 3.2: 1, 3.3:1, 3.4:1, 3.5:1, 3.6: 1, 3.7: 1, 3.8: 1, 3.9:1, 4: 1, 4.1: 1, 4.2: 1, 4.3: 1, 4.4: 1, 4.5: 1, 4.6: 1, 4.7:1, 4.8:1, 4.9:1, 5:1, 5.1: 1, 5.2: 1, 5.3: 1, 5.4:1, 5.5: 1, 5.6: 1, 5.7: 1, 5.8: 1, 5.9: 1, and 6: 1, or any range thereof.

[0049] In another aspect, the solution resides in reacting calcium sulfate (CaSCM) with carbon dioxide (CO2), and a source of ammonia. In some instances, the reaction produces ammonium sulfate and calcium carbonate. This reaction scheme provides the benefit of utilizing both carbon dioxide, including from industrial vent sources, and gypsum, including from by-product and recycled sources, such as phosphogypsum. This can result in decreasing carbon dioxide release into the atmosphere. The carbon dioxide and gypsum utilization may concern the generation of a300332254.1 - 9 -fertilizer such as urea ammonium sulfate (Nt SCM and calcium carbonate (CaCCh) that can be used together or separated and used in production of additional fertilizers.I. Product Comprising Ammonium Sulfate and Calcium Carbonate

[0050] Certain embodiments herein concern a product comprising ammonium sulfate ((Nt SCM) and calcium carbonate (CaCCh). Certain aspects involve synthesis of the nutrient complex using natural sources of ingredients, such as CaSCM and CO2. In addition to these feed sources, a source of ammonia is also used in some embodiments, such as green ammonia or blue ammonia.

[0051] The product, which may be a fertilizer, can contain ammonium sulfate encapsulating at least a portion of the calcium carbonate. The ratio of these elements present in the fertilizer may be tailored to specific applications. In some embodiments, at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43,44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69,70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95,96, 97, 98, 99, 99.5, and 100 wt. % of the based on the total weight of the product is ammonium sulfate ((Nt SCM) and / or calcium carbonate (CaCCh).

[0052] In some aspects, the product comprises nitrogen (N), sulfur (S), carbon (C), and / or calcium (Ca). In some instances, (i) The N content of the product can be at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65,66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91,92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. %, or any range therein, by weight of the product ii) the S content of the product can be at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. %, or any range therein, by weight of the product, iii) the C content of the product can300332254.1 - 10 -be at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32,33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58,59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84,85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. %, or any range therein, by weight of the product, iv) The Ca content of the product can be at least any one of, at most any one of, equal to any one of, or between any two of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41,42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67,68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93,94, 95, 96, 97, 98, 99, 99.5, and 100 wt. %, or any range therein, by weight of the product.

[0053] The N, S, C, and / or Ca can be present as and / or sourced as a water soluble compound(s) or a water insoluble compound(s). In some instances, the N, S, C, and / or Ca can be present as salts. In some aspects, the N, S, C, and / or Ca can be present as a water soluble salt(s). The N, S, C, and / or Ca salt(s) can be in a non-hydrate and / or one or more hydrate form.

[0054] The moisture content of the dried product can be less than 1 wt. %, such as 0.1 wt. % to 0.9 wt. %, or any one of or between any two of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 wt. %, or any range thereof, based on the weight of the product, such as a fertilizer granule. As a nonlimiting example, the moisture content can be measured by drying the sample at 50 °C, for 25 min and measuring the amount of mass lost by the product after being dried.

[0055] In some particular aspects, the CaSCM can contain and / or can be obtained from phosphogypsum and / or red gypsum.

[0056] The product can be of any suitable shape. Non-limiting shapes include spherical, cuboidal, cylindrical, puck shape, oval, and oblong shapes. In some aspects, the product can be of cylindrical shape with a circular, elliptical, ovular, triangular, square, rectangular, pentagonal, or hexagonal cross section, although a cylindrical shaped core having a cross-section of other shapes can also be made. In some aspects, the product at its widest dimension can be 0.5 mm to 6 mm, or 0.5 mm to 5 mm, preferably 1 mm to 4 mm, or at least any one of, at most any one of, equal to any one of, or between any two of 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, and 6 mm. In some particular aspects, the product can have a substantially spherical shape with an average diameter 0.5 mm to 6 mm, or 0.5 mm to 5 mm, preferably 1 mm300332254.1 - 11 -to 4 mm, or at least any one of, at most any one of, equal to any one of, or between any two of 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, and 6 mm.

[0057] The product can be water and / or soil dispersible. In some aspects, a product, such as a product granule having a size of 2 mm to 4 mm prior to adding to water, can disintegrate into particles having sizes less than 1 mm, less than 0.9 mm, less than 0.8 mm, less than 0.7 mm, less than 0.6 mm, less than 0.5 mm, less than 0.4 mm, or less than 0.3 mm, within 1 minute of adding the product to water at a pH 7, under stirring at a rate 90 rpm to 110 rpm, at an ambient temperature.

[0058] The product can have a compositional make-up that is substantially homogeneous. In some instances, a compositional make-up for a 1 mm x 1 mm x 1 mm cube at any position of the mixture can be similar (within ± 20 %, or ± 10 %, or ± 5 %, or ± 3 %, ± 2 %, or ± 1 %, or ± 0.5 %) to that of a 1 mm x 1 mm x 1 mm cube at any other position of the mixture. In some instances, the ammonium sulfate (NH^SCM encapsulates, coats, or is coated by another ingredient and / or fertilizer, such as calcium carbonate CaCCh. As a non-limiting example, ammonium sulfate (NH4)2SO4 may encapsulate CaCCh. In some instances, the product further contains water, calcium sulfate (CaSCM), ammonia (NH3), ammonium hydroxide (NH4OH), urea (CO(NH2)2), ammonium sulfate ((NFU SC ), and / or calcium carbonate (CaCCh,).

[0059] In some aspects, the product of the reactions and / or the starting materials of the reactions can be adjusted to fit the needs of a consumer, a plant, a soil, a water, or a combination thereof. As a non-limiting example, a nitrogen, sulfur, calcium fertilizer (N+SCa) grade can be about 12: 13:17 when the fertilizer (N+SCa) grade product comprises 1: 1 molar ratio of (bT SCM to CaCCh. In some instances, the fertilizer (N+SCa) grade can be about 15:17: 11, when the fertilizer (N+SCa) grade product comprises 2:1 molar ratio of (NH4)2SO4 to CaCCh. In some instances, the fertilizer (N+SCa) grade can be about 18:20:6 when the fertilizer (N+SCa) grade product comprises 4: 1 molar ratio of (NH4)2SO4 to CaCCh. In some aspects, the fertilizer (N+SCa) grade product may comprises (NH4)2SO4 to CaCCh in a molar ratio of 1 : 1 to 6: 1 , such as at, greater than, less than, or between 1: 1, 1.1:1, 1.2: 1, 1.3:1, 1.4: 1, 1.5:1, 1.6: 1, 1.7:1, 1.8: 1, 1.9:1, 2:1, 2.1: 1, 2.2: 1, 2.3: 1, 2.4: 1, 2.5: 1, 2.6: 1, 2.7:1, 2.8: 1, 2.9:1, 3: 1, 3.1:1, 3.2: 1, 3.3:1, 3.4:1, 3.5: 1, 3.6:1, 3.7: 1, 3.8: 1, 3.9: 1, 4:1, 4.1:1, 4.2: 1, 4.3: 1, 4.4: 1, 4.5: 1, 4.6: 1, 4.7: 1, 4.8: 1, 4.9: 1, 5: 1, 5.1: 1, 5.2: 1, 5.3:1, 5.4: 1, 5.5: 1, 5.6: 1, 5.7: 1, 5.8:1, 5.9:1, and 6:1, or any range thereof.

[0060] In some aspects, additional fertilizer substances can be included or excluded in the product. If included, additional fertilizers can be chosen based on the particular needs of certain300332254.1 - 12 -types of soil, climate, or other growing conditions to maximize the efficacy of the product in enhancing plant growth and crop yield. Additional additives may also be included or excluded in the product. Non-limiting examples of additives that can be included or excluded from the product of the present invention include additional nitrogen nutrients, phosphorus nutrients, potassium nutrients, additional micronutrients, additional secondary nutrients, pH adjusters, buffers, binders, fillers, and / or inhibitors. The micronutrient can be copper, iron, chloride, manganese, molybdenum, or nickel, or any combinations thereof. The nitrogen nutrient can be urea, ammonium nitrate, ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea-formaldehyde, ammonium chloride, and potassium nitrate. In some aspects, the additional secondary nutrients may include lime and / or superphosphate. In some instances, the additional fertilizer substances and / or the additional additives are contained in an optional coating at least partially covering the product.

[0061] In some instances, the inhibitors include nitrification inhibitors and / or urease inhibitors. Suitable nitrification inhibitors include, but are not limited to, 3,4-dimethylpyrazole phosphate (DMPP), dicyandiamide (DCD), thiourea (TU), 2-chloro-6-(trichloromethyl)-pyridine (Nitrapyrin), 5-ethoxy-3-trichloromethyl-l,2,4-thiadiazol, which is sold under the tradename Terrazole®, by OHP Inc., USA, 2-amino 4-chloro 6-methyl pyrimidine (AM), 2- mercaptobenzothiazole (MBT), or 2-sulfanilamidothiazole (ST), and any combination thereof. In one aspect, a nitrification inhibitor can comprise DMPP, DCD, TU, nitrapyrin, 5-ethoxy-3- trichloromethyl-l,2,4-thiadiazol, AM, MBT, or ST, or a combination thereof. In some embodiments, a fertilizer composition can comprise NBTPT, DMPP, TU, DCD, PPDA, nitrapyrin, 5-ethoxy-3-trichloromethyl-l,2,4-thiadiazol, AM, MBT, ST, or a combination thereof.

[0062] In some instances, a binder includes a phosphate, a polyphosphate, a biodegradable polymer, or a wax, or a combination thereof. Suitable waxes include, but are not limited to, vegetable waxes, high melt waxes, ethylene bis(stearamide) wax, paraffin waxes, polyethylene based waxes, and olefin waxes. Suitable phosphates include, but are not limited to, diammonium phosphate, and monoammonium phosphate. Suitable polyphosphates include, but are not limited to, ammonium polyphosphate. Suitable biodegradable polymers include, but are not limited to, polyacrylamide, polyacrylic acid, polyacrylonitrile, biodegradable polylactic acid and other biodegradable polymeric material such as polylactic acid, poly(3 -hydroxypropionic acid), polyvinyl alcohol, poly e-caprolactone, poly L-lactide, poly butylene succinate, and biodegradable300332254.1 - 13 -starch based polymers. The binder can include plaster of Paris, flour, starch, gluten, kaolin, bentonite, colloidal silica, or combinations thereof. Suitable flours include, but are not limited to, rice flour, wheat flour, and bleached wheat flour. Suitable starches include, but are not limited to, dextrin modified starches.

[0063] In some instances, pH buffers include MgO, KH2PO4, NaHCCh, chalk powder, aluminum, magnesium hydroxide, aluminum hydroxide / magnesium hydroxide co-precipitate, aluminum hydroxide / sodium bicarbonate co-precipitate, calcium acetate, calcium bicarbonate, calcium borate, calcium carbonate, calcium bicarbonate, calcium citrate, calcium gluconate, calcium hydroxide, dibasic sodium phosphate, dipotassium hydrogen phosphate, dipotassium phosphate, disodium hydrogen phosphate, magnesium acetate, magnesium borate, magnesium bicarbonate, magnesium carbonate, magnesium hydroxide, magnesium lactate, magnesium oxide, magnesium phosphate, magnesium silicate, magnesium succinate, magnesium tartrate, potassium acetate, potassium carbonate, potassium bicarbonate, potassium borate, potassium citrate, potassium metaphosphate, potassium phthalate, potassium phosphate, potassium polyphosphate, potassium pyrophosphate, potassium succinate, potassium tartrate, sodium acetate, sodium bicarbonate, sodium borate, sodium carbonate, sodium citrate, sodium gluconate, sodium hydrogen phosphate, sodium hydroxide, sodium lactate, sodium phthalate, sodium phosphate, sodium polyphosphate, sodium pyrophosphate, sodium tartrate, sodium tripolyphosphate, synthetic hydrotalcite, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, tripotassium phosphate, trisodium phosphate, and trometamol, and combinations thereof.

[0064] The product described herein can be comprised in a composition useful for application to soil, such as a fertilizer. In some aspects, in addition to the fertilizer described herein, the composition may include other fertilizer compounds, micronutrients, primary nutrients, urea, additional nitrogen nutrients, insecticides, herbicides, or fungicides, or combinations thereof. The fertilizer described herein can also be included in a blended composition comprising other fertilizers. The other fertilizer can be urea, monoammonium phosphate (MAP), diammonium phosphate (DAP), muriate of potash (MOP), monopotassium phosphate (MKP), triple super phosphate (TSP), rock phosphate, single super phosphate (SSP), ammonium sulfate, and the like.

[0065] A fertilizer, formed into a fertilizer granule, can have desirable physical properties such as desired levels of abrasion resistance, granule strength, pelletizability, hygroscopicity, granule shape, and size distribution. In some aspects, The fertilizer granule can have a crush strength above300332254.1 - 14 -I.5 kgf, such as above 1.8 kgf, such as 2 kgf to 6 kgf, or at least any one of, equal to any one of, or between any two of 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, and 6 kgf. Bulk density of the fertilizer granules can be 1 g / cc to 1.2 g / cc, or at least any one of, at most any one of, equal to any one of, or between any two of 1, 1.02, 1.04, 1.06, 1.08, 1.1, 1.12, 1.14, 1.16, 1.18, and 1.2 g / cc. In some aspects, 10 mg or more, such as 10 mg to 40 mg, or at least any one of, at most any one of, equal to any one of, or between any two of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40 mg of the fertilizer can dissolve in 1 ml of water at a pH 7, under stirring at a rate 90 to 110 rpm, and at an ambient temperature, within 5 minutes of adding 100 mg of the fertilizer to the water. In some aspects, the fertilizer is capable of losing less than 0.13 wt. %, such as 0.02 % to 0.12 wt. %, or at most any one of, equal to any one of, or between any two of 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, and 0.12 wt. % in an attrition loss test. Attrition loss can be measured using the following attrition loss test.

[0066] Attrition loss test: A plurality of sieved fertilizer granules with individual size 2 to 4 mm, and total volume 100 cm3is weighed (Wl) and is placed into the test drum along with the 50 stainless steel balls having a total weight of 100 gm. The drum is closed and rotated for 10 min at 30 rpm. Then, the steel balls are separated from the sample and the material is screened over 2 mm sieve using a sieve shaker. The total weight of the granules over 2 mm are then re-weighed (W2). Results are calculated in terms of % weight loss using the formula:, . . . weight of sample remained on 2 mm sieve ((IV2)) . > _Weight loss due to attrition (wt. %) = — - - - - - - — — - — - X 100 intial weight of the sample (Wt)II. Method of Producing and Separating Ammonium Sulfate

[0067] Certain aspects herein utilize calcium sulfate, such as phosphogypsum, for production of calcium carbonate (CaCCh) and / or ammonium sulfate ((NH4)2SO4). In certain embodiments, CO2 is utilized for production of the calcium carbonate. Therefore certain aspects allows for utilization of both calcium sulfate and CO2 with the simultaneous production of a first product comprising CaCCh and(NH4)2SO4).

[0068] The reaction of CaSO4and CO2, in some embodiments, comprises one step or multiple steps, such as the reaction of gypsum with the CO2 and a source of ammonia as the non-limiting example reaction (1)(1) CaSO4+ CO2 + 2NH3+ H2O CaCO3J, + (NH4)2SO4300332254.l - 15 -

[0069] In some instances, the first product comprises a solution and / or a gel of CaCOi and (Nt SO4. In some instances, separating ammonium sulfate ((Nt SCM) from the calcium carbonate (CaCCh) in another step provides a second product comprising ammonium sulfate ((Nt SCM) and calcium carbonate (CaCCh). In some instances, the first product is contacted with additional ammonium sulfate to form an ammonium sulfate-enriched first product having a greater concentration of ammonium sulfate than the first product. In some aspects, ammonium sulfate is separated from the ammonium sulfate-enriched first product to form a separated ammonium sulfate and a second product. In some instances, the additional ammonium sulfate comprises at least a portion of the separated ammonium sulfate. In some instances, additional ammonium sulfate may be added to the (NH4)2SO4 / CaCO3 solution and / or a gel in one or more forms. Additional ammonium sulfate can be added as a solid form. In some instances, additional ammonium sulfate can be added as a powder form. In some instances, additional ammonium sulfate can be added in the form of a melted liquid. In some instances, additional ammonium sulfate can be added as a solution form. In some instances, separating at least a portion of the ammonium sulfate from the ammonium sulfate-enriched first product comprises separating by distillation and / or filtration.

[0070] The reactions (1) and / or separation steps can occur at ambient temperature or any temperature at, between, above, below, or range of 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, or 65°C, or any range thereof. In some aspects, reactions (1) and / or separation steps can occur at approximately 5 to 25 bar such as, greater than, less than, or between any one of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 bar, or any range thereof. The reaction (1) and / or separation step can be performed in a continuous reaction or as a batch. The reaction (1) and / or separation can be performed for at, between, above, below, or range of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59 minutes, and / or 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 hours, and / or 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 days, or any range thereof. The feeds, reactants, products, etc. can be transported or moved into, out of, and / or through the system at a rate of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27,28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53,54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79,300332254.1 - 16 -80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320,330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510,520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700,710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890,900, 910, 920, 930, 940, 950, 960, 970, 980, 990, or 1000 g / minute, kg / minute, tons / minute, or any range thereof. The feeds, reactants, products, etc. can be provided, obtained, and / or transported at a pressure of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, and / or 50 bar, or any range thereof.

[0071] In a further step, the method may include recycling a portion of the separated ammonium sulfate back for use as the additional ammonium sulfate.

[0072] The source of ammonia, can in some instances be one or more of a solution of ammonium hydroxide, ammonium, ammonium carbonate, ammonia gas, succinimide, and / or phthalimide. The products of the reaction of calcium sulfate (CaSCM), carbon dioxide (CO2), and a source of ammonia, can in some instances also produce water, calcium sulfate (CaSCM), ammonia (NH3), ammonium hydroxide (NH4OH), ammonium sulfate ((NFU SC ), and / or calcium carbonate (CaCCh).

[0073] Referring to The Figure, the disclosed embodiment scheme demonstrates simultaneous utilization of CO2 and CaSCM producing useful products such as ammonium sulfate (NF SCM. and CaCCh. In some instances, calcium carbonate and / or ammonium sulfate can be removed during the process, and can be used as a starting material for other products, including a fertilizer, and / or blended with other compositions, including those to generate a fertilizer. The system 100 can include a first reactor 102 and a separator 104. The feed mixture ingredients 106, which can include calcium sulfate (CaSCM), carbon dioxide (CO2), and a source of ammonia, can be added in combination or separately to the first reactor 102. All or a portion of feed mixture 106 can be reacted in the first reactor 102 to generate a first reaction product 108, which can comprise a mixture of ammonium sulfate ((NF SCM) and calcium carbonate (CaCCh). In some instances, first reaction product 108 is a solution and / or a gel. In some non-limiting instances, a portion of the calcium carbonate 112 may be precipitated and separated out from the ammonium sulfate. In some instances, the separation of all or a portion of the ammonium sulfate ((NF SCM) occurs in300332254.1 - 17 -a separator 104. Mixture 108 can comprise the first reaction product that has optionally at least partially been purified by removal of at least some of the calcium carbonate. Mixture 108 can be delivered to the separator 104. In some instances, additional ammonium sulfate 116 may be added to the first product. All or a portion of ammonium sulfate 116 can be contacted in the separator 104 to generate a second reaction product 110, which can comprise ammonium sulfate and calcium carbonate, and can generate a separated ammonium sulphate 118. In some instances, the system is capable of recycling a portion of the separated ammonium sulfate 118 back to the separator 104 and / or first reactor 102. In some aspects, the recycled ammonium sulfate is delivered via a conduit. In some instances, additional ammonium sulfate 116 may comprise separated ammonium sulfate 118. In some instances, the calcium carbonate is separated from the ammonium sulfate in such a way as to generate the required ratios of ammonium sulfate and calcium carbonate in the second product. In some instances, the calcium carbonate and ammonium sulfate are not separate. In some instances, the separation occurs between the reactor and the separator, or in an additional separator, such as a second separator (not shown). The second reaction product 110 such as ammonium sulfate and calcium carbonate which has been at least partially purified by removing at least a portion of the ammonium sulfate. In some instances, all or a portion of the separated ammonium sulfate 118 can be combined with the additional ammonium sulfate 116 (not shown). In some instances, all or a portion of the second reaction product 110 can be removed from the system. All or a portion of the calcium carbonate 112 can be removed from the system. In some instances, the second reaction product 110 can further comprise water, calcium sulfate (CaSCM), ammonia (NH3), ammonium hydroxide (NH4OH), ammonium sulfate ((NFU SC ), and / or calcium carbonate (CaCCh). In some aspects, the separated ammonium sulfate 118 is dried to a solid, such as a powder. In some aspects, the additional ammonium sulfate 116 is a solid, such as a powder.

[0074] In some instances, the disclosed embodiment scheme does not include production of phosphogypsum or gypsum.III. Methods of Using Ammonium Sulfate and Calcium Carbonate

[0075] The product and / or compositions containing ammonium sulfate and calcium carbonate may be used as fertilizer, or fertilizer blends containing the ammonium sulfate and calcium carbonate. The fertilizer of the present disclosure can be used in methods of increasing the amount of one or more plant nutrients in soil and of enhancing plant growth. In some instances, CaCCh300332254.1 - 18 -and / or (NH^SCM can be used as a fertilizer or fertilizer component, such as use of CaCOi for acid soils.

[0076] Such methods can include applying to the soil an effective amount of a composition and / or blend containing the fertilizer of the present invention. The method may include increasing the growth and yield of crops, trees, ornamentals, etc., such as, for example, palm, coconut, rice, wheat, corn, barley, oats, and / or soybeans. The method can include applying the fertilizer blend of the present invention to at least one of a soil, an organism, a liquid carrier, a liquid solvent, etc. The composition(s) and / or fertilizer blends(s) containing the fertilizer can be applied to plants and / or soil as a top dressing fertilizer, basal fertilizer, and / or through any suitable method of application.

[0077] Non-limiting examples of plants that can benefit from the fertilizer of the present invention include vines, trees, shrubs, stalked plants, ferns, etc. The plants may include orchard crops, vines, ornamental plants, food crops, timber, and harvested plants. The plants may include Gymnosperms, Angiosperms, and / or Pteridophytes.

[0078] In some instances, especially when produced on-site and near end-use sites, the filtrate of ammonium sulfate and calcium carbonate can be used directly as a liquid fertilizers for direct field applications in foliar spray or drip irrigation methods.

[0079] The effectiveness of compositions comprising the products of the present invention can be ascertained by measuring the amount of calcium and optionally other nutrients in the soil at various times after applying the product to the soil. It is understood that different soils have different characteristics, which can affect the stability of the nutrients in the soil. The effectiveness of a fertilizer composition can also be directly compared to other fertilizer compositions by doing a side-by-side comparison in the same soil under the same conditions.EXAMPLES

[0080] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.300332254.1 - 19 -Example 1

[0081] 10 g CaSCM was loaded to a Parr reactor having a volume of 200 ml. To the reactor17.13 g NH4OH (30% wt concentration of NH4OH) solution was added, and the reactor was fed with CO2 with a flow rate of 15 cc / min. A reaction occurred and was continued for 2 hours at 20 bar pressure and 50 °C. After two hours the reaction was stopped and the reaction product was filtered, which required a filtration time of 60 min. The product, comprising CaCCh and (NPU SCM was separated. The CaSCM conversion was found to be 95%.Example 2

[0082] Example 2 was carried out as described in Example 1 , but with the addition of 5 g dried ammonium sulfate to the reaction product of ammonium sulfate and calcium carbonate prior to its filtration step. The filtration time in this case only required 30 min., which is 50% less than the required filtration time of the reaction product of Example 1.Example 3Prophetic Example

[0083] CaSCM and NH4OH can be loaded into a Parr reactor to react with CO2 gas introduced with 25 cc / min flow at 20 bar through the Parr reactor. The reactor can be heated to 60°C inside of the reactor and a reaction can continue for 2 hours. The reactor can be cooled to room temperature. The reaction can form a first product containing ammonium sulfate ((NIE SCM) and calcium carbonate (CaCCE) in a solution / gel form. The first product can be moved to a separator unit, where an additional amount of ammonium sulfate can be added to generate a second product and a separated ammonium sulfate. In some instances, the second product will contain both ammonium sulfate ((NIE SCM) and calcium carbonate (CaCCh). In some instances, the additional ammonium sulfate may comprise at least a portion of the separated ammonium sulfate. In some instances, the second product can further contain water, calcium sulfate (CaSCM), ammonia (NH3), and / or ammonium hydroxide (NH4OH). In some instances, the CaCCh is separated to form a product containing (NIE SCM. In some instances, fertilizer product is generated comprising a required ratio of ammonium sulfate ((NFU SCM) and calcium carbonate (CaCCh).* * *

[0084] All of the methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of300332254.1 - 20 -this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.300332254.1 - 21 -

Claims

CLAIMS1. A method of producing ammonium sulfate and calcium carbonate, the method comprising the steps of:(a) contacting calcium sulfate (CaSCM) with carbon dioxide (CO2) and a source of ammonia to generate a first product comprising calcium carbonate (CaCCh) and ammonium sulfate ((NH4)2SO4);(b) contacting the first product with additional ammonium sulfate to form an ammonium sulfate-enriched first product having a greater concentration of ammonium sulfate than the first product; and(c) separating at least a portion of the ammonium sulfate from the ammonium sulfate- enriched first product to form a separated ammonium sulfate and a second product, wherein the additional ammonium sulfate comprises at least a portion of the separated ammonium sulfate.

2. The method of claim 1, wherein the first product comprises a solution and / or a gel.

3. The method of any one of claims 1 to 2, wherein the additional ammonium sulfate comprises solid ammonium sulfate.4 The method of claim 3, wherein the solid ammonium sulfate comprises a powder.

5. The method of any one of claims 1 to 4, wherein the separating at least a portion of the ammonium sulfate from the ammonium sulfate-enriched first product comprises separating by distillation.

6. The method of any one of claims 1 to 5, wherein the second product comprises calcium carbonate and ammonium sulfate.

7. The method of claim 6, wherein a computer processing unit controls a ratio of the calcium carbonate to the ammonium sulfate in the second product, the computer processing unit controlling an amount of additional ammonium sulfate contacting the first product.300332254.1 - 22 -8. The method of any one of claims 1 to 7, further comprising drying the second product to form a solid second product.

9. The method of any one of claims 1 to 8, wherein: the calcium sulfate is a waste gypsum and / or a recycled gypsum, preferably wherein the calcium sulfate is phosphogypsum and / or red gypsum; the source of ammonia is one or both of ammonia (NH3) and ammonium hydroxide (NH4OH); and / or a source of the carbon dioxide comprises waste gas from an industrial plant and / or flue gas.

10. The method of any one of claims 1 to 9, wherein the second product further comprises calcium sulfate, ammonia, and / or ammonium hydroxide.

11. The method of any one of claims 1 to 10, wherein: the contacting calcium sulfate with carbon dioxide and a source of ammonia occurs at approximately 30°C to 65°C; and / or the contacting the first product with additional ammonium sulfate occurs at approximately 30°C to 65°C.

12. The method of any one of claims 1 to 11, wherein: the contacting calcium sulfate with carbon dioxide and a source of ammonia occurs at approximately 5 to 25 bar; and / or the contacting the first product with additional ammonium sulfate occurs at approximately 5 to 25 bar.

13. The method of any one of claims 1 to 12, further comprising contacting the second product with a micronutrients and / or a nitrogen fertilizer other than ammonium sulfate.

14. A system for producing ammonium sulfate and calcium carbonate, the system comprising: a reactor capable of receiving calcium sulfate (CaSCM), carbon dioxide (CO2), and a source of ammonia, wherein the reactor is capable of providing conditions to generate a300332254.1 - 23 -first product comprising calcium carbonate (CaCCh) and ammonium sulfate ((NH4)2SO4); a separator in fluid communication with the reactor, the separator capable of separating at least a portion of the ammonium sulfate from the first product to form a separated ammonium sulfate and a second product; and a conduit in fluid communication with the separator, the conduit capable of transporting at least a portion of the separated ammonium sulfate to contact the first product between the reactor and the separator or at the separator.

15. The system of claim 14, wherein the reactor is capable of receiving and reacting carbon dioxide from a flue gas and / or a waste gas from an industrial plant, preferably wherein the carbon dioxide from the flue gas and / or waste gas is not purified to separate or concentrate the carbon dioxide in the flue gas and / or waste gas before reacting to form the calcium carbonate.300332254.1 - 24 -

Images