Preparation method of calcium nutrient supporting carbon neutralization

Abstract

Methods and systems for capturing carbon dioxide and utilizing calcium sulfate to produce useful products are disclosed.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of European Application No. 22182217.4, filed on June 30, 2022, which is incorporated herein by reference in its entirety. Background of the Invention I. Technical field

[0003] The present disclosure generally relates to methods of producing fertilizer using carbon dioxide and phosphogypsum. II. Background Technology

[0004] Over the past decade, the world has become increasingly aware of the adverse environmental impacts of handling process industries such as phosphogypsum. In this case, PG is considered waste and needs to be disposed of by dumping it on land or discharging it into the ocean. Both of these disposal methods can have adverse effects on the environment.

[0005] Furthermore, reducing CO2 emissions is currently one of the top priorities for many industries. Chemical utilization of CO2 by reducing it to CO and participating in chemical reactions requires excessive energy consumption. This is one of the reasons why many chemical companies are currently working to reduce CO2 emissions by storing CO2 deep underground. Summary of the invention

[0006] Solutions to at least some of the above problems have been discovered, including the efficient utilization of phosphogypsum and carbon dioxide. In one aspect, the solution is to react calcium sulfate (CaSO4) with carbon dioxide (CO2) and an ammonia source such as one or both of ammonia (NH3) and ammonium hydroxide (NH4OH), and then decompose the resulting ammonium sulfate, as shown in non-limiting example reactions (1) and (2), respectively. This reaction scheme provides the benefits of utilizing carbon dioxide, including carbon dioxide from waste sources, and phosphogypsum, including phosphogypsum from waste and recycled sources. This can reduce carbon dioxide released into the atmosphere while generating useful products. The utilization of carbon dioxide and phosphogypsum may involve the production of fertilizers, such as calcium carbonate (CaCO3) or ammonium sulfate ((NH4)2SO4), and / or the production of acids, such as sulfuric acid (H2SO4) that can be used to produce phosphoric acid (H2PO4).

[0007] (1)CaSO4.2H2O+CO2+2NH3→CaCO3+(NH4)2SO4+H2O

[0008] (2) (NH4)2SO4→2NH3+H2SO4

[0009] Certain aspects relate to a final product containing a mixture comprising, consisting essentially of, or consisting of any of the above chemicals, including CaCO 3. Embodiments of the present disclosure are improvements over known methods of producing fertilizers, including fertilizers comprising, consisting essentially of, or consisting of CaCO 3, including by involving the use of CO 2 and / or gypsum such as phosphogypsum.

[0010] Certain embodiments provide for utilizing (eg, by recycling) large amounts of CO2 for synthesizing complex nutrients, such as (NH4)2SO4 / K2SO4.

[0011] Certain aspects relate to a method for capturing CO2 and using calcium sulfate to prepare sulfuric acid. The method may include steps (a), (b) and / or (c). In step (a), calcium sulfate (CaSO4) is contacted with carbon dioxide (CO2) and an ammonia source such as one or both of ammonia (NH3) and ammonium hydroxide to produce a first product comprising calcium carbonate (CaCO3) and ammonium sulfate ((NH4)2SO4). In step (b), the (NH4)2SO4 in the first product is decomposed into NH3 and sulfuric acid (H2SO4) by contacting the (NH4)2SO4 with a catalyst such as an additional acid. In step (c), the H2SO4 generated in step (b) is contacted with calcium phosphate (Ca3(PO4)2) to produce phosphoric acid (H3PO4) and CaSO4.

[0012] In some aspects, the additional acid in step (b) comprises H2SO4 or is composed of H2SO4. In some aspects, the source of the CaSO4 in step (a) comprises waste gypsum and / or recycled gypsum. In some aspects, the source of the CO2 in step (a) comprises waste gas and / or flue gas from industrial facilities. In some aspects, the source of the CaSO4 in step (a) comprises phosphogypsum. In some aspects, step (a) is carried out at about 50°C to 70°C. In some aspects, CaCO3 is separated from the first product before step (b). In some aspects, the method comprises step (d). In step (d), the separated CaCO3 is combined with plant nutrients to form fertilizer. In some aspects, the separated CaCO3 is dried. In some aspects, at least a portion of the NH3 generated in step (b) is used as at least a portion of the NH3 used in step (a). In certain aspects, at least a portion of the H2SO4 generated in step (b) is used as at least a portion of the H2SO4 to generate phosphogypsum.

[0013] In certain aspects, at least a portion of the generated phosphogypsum is used as a source of CaSO 4 in step (a).

[0014] Some aspects relate to a system for capturing CO2 and using calcium sulfate (CaSO4) to prepare sulfuric acid (H2SO4). In some aspects, the system includes or consists of element (a), element (b) and / or element (c). Element (a) may include a first reactor, which can receive CaSO4, CO2, and one or both of NH3 and NH4OH, and provide conditions to produce a product comprising CaCO3 and (NH4)2SO4. Element (b) may include a second reactor, which can decompose the (NH4)2SO4 produced by reactor (a) into H2SO4 and NH3. Element (c) may include a device capable of separating CaCO3 from the product produced in the first reactor. In some aspects, the system includes element (a) and element (b) without element (c). In some aspects, the system includes element (a), element (b) and element (c). In some aspects, the first reactor and the second reactor are identical reactors. In other aspects, the first reactor and the second reactor are different reactors. In some embodiments, the system includes a device connecting the first reactor and the second reactor. In some aspects, the system includes a third reactor capable of receiving H2SO4 and calcium phosphate (Ca3(PO4)2) and providing conditions to produce CaSO4 and phosphoric acid (H3PO4). The first reactor, the second reactor, and the third reactor can be the same reactor, or in some aspects, the first reactor, the second reactor, and the third reactor can be different reactors. In some aspects, the first reactor and the third reactor are the same reactor. In some aspects, the second reactor and the third reactor are the same reactor. In some aspects, the first reactor is capable of receiving and reacting CO2 from flue gas and / or waste gas from an industrial facility. In some aspects, the first reactor is capable of receiving and reacting CO2 from flue gas and / or waste gas from an industrial facility, wherein the CO2 from the flue gas and / or waste gas is not purified to separate or concentrate the CO2 in the flue gas and / or waste gas before reacting to form CaCO3.

[0015] The following aspects 1 to 23 of the present invention are also disclosed.

[0016] Aspect 1 is a method for capturing CO2 and using calcium sulfate (CaSO4) to produce sulfuric acid (H2SO4), the method comprising the following steps:

[0017] (a) contacting calcium sulfate (CaSO4) with 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 calcium carbonate (CaCO3) and ammonium sulfate ((NH4)2SO4); and

[0018] (b) decomposing (NH4)2SO4 in the first product into NH3 and sulfuric acid (H2SO4) by contacting (NH4)2SO4 with a catalyst.

[0019] Aspect 2 is the method according to aspect 1, further comprising:

[0020] (c) contacting the H2SO4 produced in step (b) with calcium phosphate (Ca3(PO4)2) to produce phosphoric acid (H3PO4) and CaSO4.

[0021] Aspect 3 is the method of aspect 1 or 2, wherein the catalyst is an additional acid, preferably H2SO4.

[0022] Aspect 4 is the method of any one of aspects 1 to 3, wherein the source of CaSO4 in step (a) comprises waste gypsum and / or recycled gypsum.

[0023] Aspect 5 is the method of any one of aspects 1 to 4, wherein the source of CO2 in step (a) comprises waste gas and / or flue gas from an industrial facility.

[0024] Aspect 6 is the method of any one of aspects 1 to 5, wherein the source of CaSO4 in step (a) comprises phosphogypsum.

[0025] Aspect 7 is the method of any one of aspects 1 to 6, wherein step (a) occurs at about 50°C to 70°C.

[0026] Aspect 8 is the method of any one of Aspects 1 to 7, further comprising separating CaCO3 from the first product before step (b).

[0027] Aspect 9 is the method according to aspect 8, further comprising:

[0028] (d) combining the separated CaCO3 with plant nutrients to form a fertilizer.

[0029] Aspect 10 is the method of any one of Aspects 8 and 9, further comprising drying the separated CaCO3.

[0030] Aspect 11 is the method of any one of aspects 1 to 10, wherein at least a portion of the NH 3 generated in step (b) is used as at least a portion of the NH 3 used in step (a).

[0031] Aspect 12 is the method of any one of aspects 1 to 11, wherein at least a portion of the H 2 SO 4 generated in step (b) is used as at least a portion of the H 2 SO 4 for generating phosphogypsum.

[0032] Aspect 13 is the method of aspect 12, wherein at least a portion of the generated phosphogypsum is used as a source of CaSO4 in step (a).

[0033] Aspect 14 is a system for capturing CO2 and using calcium sulfate (CaSO4) to produce sulfuric acid (H2SO4), the system comprising:

[0034] (a) a first reactor capable of receiving CaSO4, CO2 and one or both of NH3 and NH4OH and providing conditions to produce a product comprising CaCO3 and (NH4)2SO4;

[0035] (b) a second reactor capable of decomposing the (NH4)2SO4 produced in reactor (a) into H2SO4 and NH3; and

[0036] (c) Optional means capable of separating CaCO3 from the product produced in the first reactor.

[0037] Aspect 15 is the system of aspect 14, wherein the first reactor and the second reactor are the same reactor.

[0038] Aspect 16 is the system of aspect 14, wherein the first reactor and the second reactor are different reactors.

[0039] Aspect 17 is the system of aspect 16, further comprising a device connecting the first reactor and the second reactor.

[0040] Aspect 18 is the system of any one of Aspects 14 to 17, further comprising a third reactor capable of receiving H2SO4 and calcium phosphate (Ca3(PO4)2) and providing conditions to produce CaSO4 and phosphoric acid (H3PO4).

[0041] Aspect 19 is the system of any of aspects 14 to 18, wherein the third reactor and the second reactor are the same reactor.

[0042] Aspect 20 is the system of any one of aspects 14 to 19, wherein the third reactor, the second reactor, and the first reactor are the same reactor.

[0043] Aspect 21 is the system of any one of aspects 14 to 20, wherein the third reactor, the second reactor, and the first reactor are different reactors.

[0044] Aspect 22 is the system of any one of aspects 14 to 21, wherein the first reactor is capable of receiving and reacting CO 2 in flue gas and / or exhaust gas from an industrial facility.

[0045] Aspect 23 is a system described in any of Aspects 14 to 22, wherein the first reactor is capable of receiving and reacting CO2 from flue gas and / or exhaust gas from an industrial facility, wherein the CO2 from the flue gas and / or exhaust gas is not purified to separate or concentrate the CO2 in the flue gas and / or exhaust gas before reacting to form CaCO3.

[0046] The term "fertilizer" is defined as a material applied to soil or plant tissue to provide one or more plant nutrients necessary or beneficial to plant growth and / or a stimulant or enhancer that promotes or enhances plant growth.

[0047] The term "granule" may include solid materials. Granules may have a variety of shapes, non-limiting examples of which include spheres, discs, ellipses, rods, rectangles, or random shapes.

[0048] The term "particle" may include solid materials having a maximum dimension of less than a millimeter.

[0049] The term "particulate" or "powder" may include a plurality of particles.

[0050] As used herein, the term "about" or "approximately" is defined as close to what is understood by one of ordinary skill in the art. In a non-limiting embodiment, the term is defined as within 10% deviation, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0051] The terms "weight %", "volume %" or "mole %" refer to the weight percentage, volume percentage or mole percentage of a component based on the total weight, total volume, or total number of moles of the material containing the component, respectively. In a non-limiting example, 10 grams of a component in 100 grams of material is 10 weight %.

[0052] When an element is preceded by no quantifier and used with the terms "comprises" or "comprising", it can mean "a", but it is also consistent with "one or more", "at least one", and "one or more than one".

[0053] The phrase "and / or" means "and" or "or". For example, 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" serves as an inclusive "or".

[0054] The words "comprising," "having," "including," or "containing" are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0055] Compositions and methods of use thereof may "comprise," "consist essentially of," or "consist of" any of the ingredients or steps disclosed throughout the specification. Compositions and methods that "consist essentially of" any of the disclosed ingredients or steps limit the scope of the claims to the specific materials or steps that do not materially affect the basic and novel characteristics of the claimed invention.

[0056] 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. In addition, the compositions of the invention can be used to implement the methods of the invention.

[0057] Other purposes, features and advantages of the present invention become apparent through the following specific embodiments. However, it should be understood that the specific embodiments and specific examples, although indicating specific embodiments of the present invention, are given by way of illustration only, because various changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art according to the specific embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] The following drawings form part of this specification and are included to further illustrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in conjunction with the detailed description of specific embodiments provided herein.

[0059] Figure 1 : Schematic diagram of a system and method for capturing CO2 and using calcium sulfate in conjunction with a phosphoric acid production process according to a non-limiting example of the systems and methods disclosed herein.

[0060] Figure 2 : Schematic diagram of a system and method for capturing CO2 and using calcium sulfate according to a non-limiting example of the systems and methods disclosed herein.

[0061] Figure 3 : Schematic diagram of a system and method for capturing CO2 and using calcium sulfate according to a non-limiting example of the systems and methods disclosed herein. DETAILED DESCRIPTION

[0062] Certain aspects of the present disclosure provide advantages over existing carbon dioxide capture technologies, including through the efficient utilization of phosphogypsum. In one aspect, the solution is to react calcium sulfate (CaSO4) with carbon dioxide (CO2) and an ammonia source such as one or both of ammonia (NH3) and ammonium hydroxide (NH4OH), and then decompose the resulting ammonium sulfate. This reaction scheme provides the advantages of utilizing carbon dioxide, including carbon dioxide from waste sources, and phosphogypsum, including phosphogypsum from waste and recycled sources. This can reduce the emission of carbon dioxide into the atmosphere. The utilization of carbon dioxide and phosphogypsum may involve the production of fertilizers. In addition, certain aspects do not include the generation and / or inclusion of calcium phosphate urea, urea phosphate and / or urea calcium sulfate.

[0063] I. Fertilizer

[0064] Certain embodiments herein relate to fertilizers comprising CaCO3. Certain aspects relate to the synthesis of nutrient complexes using fertilizer ingredients of natural origin, such as CaSO4 and CO2. In addition to these feed sources, in some embodiments, ammonia sources are used, such as solutions of ammonium hydroxide, ammonium, ammonium carbonate, ammonia gas, succinimide, and / or phthalimide.

[0065] The fertilizer can be a fertilizer granule and can contain calcium (Ca) and carbon (C) in the form of carbonates. The ratio of elements in the fertilizer can be adjusted according to the specific application. In some embodiments, at least, at most, or equal to 1 weight %, 2 weight %, 3 weight %, 4 weight %, 5 weight %, 6 weight %, 7 weight %, 8 weight %, 9 weight %, 10 weight %, 11 weight %, 12 weight %, 13 weight %, 14 weight %, 15 weight %, 16 weight %, 17 weight %, 18 weight %, 19 weight %, 20 weight %, 21 weight %, 22 weight %, 23 weight %, 24 weight %, 25 weight %, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 %, 54% by weight, 55% by weight, 56% by weight, 57% by weight, 58% by weight, 59% by weight, 60% by weight, 61% by weight, 62% by weight, 63% by weight, 64% by weight, 65% by weight, 66% by weight, 67% by weight, 68% by weight, 69% by weight, 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, 75% by weight, 76% by weight, 77% by weight, 78% by weight, 79% by weight, 80% by weight %, 81 wt %, 82 wt %, 83 wt %, 84 wt %, 85 wt %, 86 wt %, 87 wt %, 88 wt %, 89 wt %, 90 wt %, 91 wt %, 92 wt %, 93 wt %, 94 wt %, 95 wt %, 96 wt %, 97 wt %, 98 wt %, 99 wt %, 99.5 wt % and 100 wt %, or in a range between any two thereof, Ca may be present in the form of calcium carbonate.

[0066] In some aspects, the fertilizer comprises Ca, nitrogen (N), phosphorus (P), potassium (K), and / or C. i) The Ca content of the fertilizer can be at least, at most, or equal to 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 %, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight, 38% by weight, 39% by weight, 40% by weight, 41% by weight, 42% by weight, 43% by weight, 44% by weight, 45% by weight, 46% by weight, 47% by weight, 48% by weight, 49% by weight %, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 99.%, 15 wt %, 16 wt %, 17 wt %, 18 wt %, 19 wt %, 20 wt %, 21 wt %, 22 wt %, 23 wt %, 24 wt %, 25 wt %, 26 wt %, 27 wt %, 28 wt %, 29 wt %, 30 wt %, 31 wt %, 32 wt %, 33 wt %, 34 wt %, 35 wt %, 36 wt %, 37 wt %, 38 wt %, 39 wt %, 40 wt %, 41 wt %, 42 wt %, 43 wt %, 44 wt %, 45 wt %, 46 wt %, 47 wt %, 48 wt %, 49 wt %, 50 wt %, 51 wt %, 52 wt %, 53 wt %, 54 wt %, 55 wt %, 56 wt %, 57 wt %, 58 wt %, 59 wt %, 60 wt %, 61 wt %, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, %, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 99.% and 100 wt %, or between any two thereof, iii) the P content of the fertilizer may be at least, at most, or equal to 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt %, 15 wt %, 16 wt %, 17 wt %, 18 wt %, 19 wt %, 20 wt %, %, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, %, 48% by weight, 49% by weight, 50% by weight, 51% by weight, 52% by weight, 53% by weight, 54% by weight, 55% by weight, 56% by weight, 57% by weight, 58% by weight, 59% by weight, 60% by weight, 61% by weight, 62% by weight, 63% by weight, 64% by weight, 65% by weight, 66% by weight, 67% by weight, 68% by weight, 69% by weight, 70% by weight, 71% by weight, 72% by weight, 73% by weight , 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 99.% and 100 wt %, or between any two thereof, iv) the K content of the fertilizer may be at least, at most, or equal to 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt %, 15 wt %, 16 wt %, 17 wt %, 18 wt %, 19 wt %, based on the total weight of the fertilizer. %, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, %, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, %, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 99.%, 15 wt %, 16 wt %, 17 wt %, 18 wt %, 19 wt %, 20 wt %, 21 wt %, 22 wt %, 23 wt %, 24 wt %, 25 wt %, 26 wt %, 27 wt %, 28 wt %, 29 wt %, 30 wt %, 31 wt %, 32 wt %, 33 wt %, 34 wt %, 35 wt %, 36 wt %, 37 wt %, 38 wt %, 39 wt %, 40 wt %, 41 wt %, 42 wt %, 43 wt %, 44 wt %, 45 wt %, 46 wt %, 47 wt %, 48 wt %, 49 wt %, 50 wt %, 51 wt %, 52 wt %, 53 wt %, 54 wt %, 55 wt %, 56 wt %, 57 wt %, 58 wt %, 59 wt %, 60 wt %, 61 wt %, 62 wt %, 63 wt %, 64 wt %, 65 wt %, 66 wt %, 67 wt %, 68 wt %, 69 wt %, %, 21 wt %, 22 wt %, 23 wt %, 24 wt %, 25 wt %, 26 wt %, 27 wt %, 28 wt %, 29 wt %, 30 wt %, 31 wt %, 32 wt %, 33 wt %, 34 wt %, 35 wt %, 36 wt %, 37 wt %, 38 wt %, 39 wt %, 40 wt %, 41 wt %, 42 wt %, 43 wt %, 44 wt %, 45 wt %, 46 wt %, 47 wt %, 48 wt %, %, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt% , 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 99.5 wt% and 100 wt%, or between any two thereof.

[0067] Ca, N, P, K and / or C can exist and / or be derived from the form of one or more than one water-soluble compound or one or more than one water-insoluble compound. In some cases, Ca, N, P, K and / or C can exist in the form of a salt. In some aspects, Ca, N, P, K and / or C can exist in the form of one or more than one water-soluble salt. One or more than one salt of Ca, N, P, K and / or C can be in the form of a non-hydrate and / or one or more than one hydrate.

[0068] The moisture content of the dried fertilizer can be 1 wt % or less, e.g., 0.1 wt % to 0.9 wt %, or any one of 0.1 wt %, 0.2 wt %, 0.3 wt %, 0.4 wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt % or 1 wt %, or between any two thereof, or in any range therein, based on the weight of the fertilizer, e.g., fertilizer granules. As a non-limiting example, the moisture content can be measured by drying the sample at 50° C. for 25 minutes and measuring the mass lost by the fertilizer after drying.

[0069] In some specific aspects, the CaSO4 can include and / or can be obtained from phosphogypsum.

[0070] Fertilizer can be any suitable shape.Non-limiting shape comprises spherical, cubic, cylindrical, disc-shaped, elliptical and rectangular.In some respects, fertilizer can be the cylinder with circular cross section, elliptical cross section, oval cross section, triangle cross section, square cross section, rectangular cross section, pentagonal cross section or hexagonal cross section, although also can manufacture the cylindrical core with other shape cross section.In some respects, the widest size of fertilizer can be 0.5mm to 6mm or 0.5mm to 5mm, preferably 1mm to 4mm, or at least, at most or equal to any one of 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 5.5mm and 6mm, or between any two thereof. In some specific aspects, the fertilizer can have a substantially spherical shape with an average diameter of 0.5 mm to 6 mm, or 0.5 mm to 5 mm, preferably 1 mm to 4 mm, or at least, at most, or equal to any one 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, or between any two thereof.

[0071] The fertilizer can be capable of being dispersed in water and / or soil. In some aspects, at ambient temperature, under stirring at a rate of 90 rpm to 110 rpm, within 1 minute of adding the fertilizer to water at a pH of 7, the fertilizer, such as fertilizer particles having a size of 2 mm to 4 mm before being added to the water, can be decomposed into particles having a size of 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.

[0072] The fertilizer may have a substantially uniform composition. In some cases, the composition of a 1 mm x 1 mm x 1 mm cube at any location in the mixture is similar to the composition of a 1 mm x 1 mm x 1 mm cube at any other location in the mixture (within ±20%, or within ±10%, or within ±5%, or within ±3%, or within ±2%, or within ±1%, or within ±0.5%).

[0073] In some respects, additional fertilizer materials may be included or excluded in the fertilizer. If included, additional fertilizers may be selected according to the special needs of certain types of soil, climate or other growth conditions to maximize the effectiveness of fertilizers in promoting plant growth and crop yield. Additional additives may also be included or excluded in the fertilizer. Non-limiting examples of additives that may be included or excluded from the fertilizer of the present invention include additional nitrogen nutrients, phosphorus nutrients, potassium nutrients, additional trace nutrients and / or additional secondary nutrients. Trace nutrients may be copper, iron, chloride, manganese, molybdenum or nickel, or any combination thereof. Nitrogen nutrients may be urea, ammonium nitrate, ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea-formaldehyde, ammonium chloride and potassium nitrate. In some respects, additional secondary nutrients may include lime and / or superphosphate. In some cases, additional fertilizer materials and / or additional additives are included in an optional coating that at least partially covers the fertilizer.

[0074] In some cases, the inhibitor includes a nitrification inhibitor and / or a urease inhibitor. Suitable nitrification inhibitors include, but are not limited to, 3,4-dimethylpyrazole phosphate (DMPP), dicyandiamide (DCD), thiourea (TU), 2-chloro-6-(trichloromethyl)-pyridine (chlorpyrifos), commercially available from OHP Inc., USA under the trade name 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercaptobenzothiazole (MBT), or 2-sulfathiazole (ST), and any combination thereof. In one aspect, the nitrification inhibitor may include DMPP, DCD, TU, chlorpyrifos, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT, or ST, or a combination thereof. In some embodiments, the fertilizer composition may include NBTPT, DMPP, TU, DCD, PPDA, chlorpyrifos, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT, ST, or a combination thereof.

[0075] In some cases, the binder includes phosphate, polyphosphate, biodegradable polymer, or wax, or a combination thereof. Suitable waxes include, but are not limited to, vegetable wax, high melting point wax, ethylene bis (stearamide) wax, paraffin, polyethylene based wax, and olefin wax. 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 polymer materials such as polylactic acid, poly (3-hydroxypropionic acid), polyvinyl alcohol, poly-ε-caprolactone, poly-L-lactide, polybutylene succinate, and biodegradable starch-based polymers. The binder may include plaster of Paris, flour, starch, gluten, kaolin, bentonite, colloidal silicon dioxide, or a combination thereof. Suitable flour includes, but is not limited to, rice flour, wheat flour, and bleached wheat flour. Suitable starch includes, but is not limited to, dextrin-modified starch.

[0076] In some cases, the pH buffer includes MgO, KH2PO4, NaHCO3, chalk powder, aluminum, magnesium hydroxide, aluminum hydroxide / magnesium hydroxide coprecipitate, aluminum hydroxide / sodium bicarbonate coprecipitate, calcium acetate, calcium bicarbonate, calcium borate, calcium carbonate, calcium bicarbonate, calcium citrate, calcium gluconate, calcium hydroxide, disodium hydrogen 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 tromethamine, and combinations thereof.

[0077] Fertilizer as herein described can be included in the composition for being applied to soil.In some respects, except fertilizer as herein described, said composition can include other fertilizer compounds, trace nutrients, major nutrients, urea, additional nitrogen nutrients, pesticides, herbicides or fungicides or its combination.Fertilizer as herein described can also be included in the mixed composition comprising other fertilizers.Other fertilizers can be urea, monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium chloride (MOP), potassium dihydrogen phosphate (MKP), triple superphosphate (TSP), phosphate rock, superphosphate (SSP), ammonium sulfate etc.

[0078] The fertilizer forming the fertilizer granules may have desired physical properties, such as desired wear resistance, granule strength, granulation, hygroscopicity, granule shape and size distribution. In some aspects, the crushing strength of the fertilizer granules may be 1.5 kgf or more, such as 1.8 kgf or more, such as 2 kgf to 6 kgf, or at least or equal to any one of 2 kgf, 2.5 kgf, 3 kgf, 3.5 kgf, 4 kgf, 4.5 kgf, 5 kgf, 5.5 kgf and 6 kgf, or between any two thereof. The bulk density of the fertilizer granules can be 1 g / cc to 1.2 g / cc, or at least, at most, or equal to any one of 1 g / cc, 1.02 g / cc, 1.04 g / cc, 1.06 g / cc, 1.08 g / cc, 1.1 g / cc, 1.12 g / cc, 1.14 g / cc, 1.16 g / cc, 1.18 g / cc and 1.2 g / cc, or between any two thereof. In some aspects, 10 mg or more of the fertilizer, such as 10 mg to 40 mg of the fertilizer, or at least, at most, or equal to any one 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, or a range between any two of the fertilizer, can be dissolved in 1 mL of water at a pH of 7 within 5 minutes of adding 100 mg of the fertilizer to the water with stirring at a rate of 90 to 110 rpm and at ambient temperature. In some aspects, the fertilizer can lose 0.13 wt% or less in an attrition loss test, such as 0.02 wt% to 0.12 wt%, or up to or equal to any one of 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.11 wt%, and 0.12 wt%, or between any two thereof. Attrition loss can be measured using the following Attrition Loss Test.

[0079] Abrasion loss test: Weigh multiple sieved fertilizer particles, with individual particles ranging from 2 mm to 4 mm in size, in a total volume of 100 cm 3(W1) and placed in the test drum along with 50 stainless steel balls with a total weight of 100gm. The drum was closed and rotated at 30rpm for 10 minutes. The steel balls were then separated from the sample and the material was sieved on a 2mm screen using a sieve shaker. The total weight of particles above 2mm was then reweighed (W2). The results were calculated in terms of weight loss % using the following formula:

[0080]

[0081] II. Methods of Capturing Carbon Dioxide and Utilizing Calcium Sulfate

[0082] In some cases, phosphoric acid is produced industrially by the reaction of calcium phosphate with sulfuric acid, which also produces calcium sulfate in the form of phosphogypsum. Calcium sulfate is produced more by weight than phosphoric acid. The production of phosphogypsum from calcium phosphate and sulfuric acid is described by the following stoichiometric equation:

[0083] Ca3(PO4)2+3H2SO4→2H3PO4+3CaSO4

[0084] Some aspects of this paper utilize calcium sulfate such as phosphogypsum to produce sulfuric acid, and the byproduct CaCO is used for acidic soils. In certain embodiments, CO is used for the production of calcium carbonate. Therefore, some aspects allow the use of calcium sulfate and CO, and sulfuric acid and CaCO are produced simultaneously, which can be used for fertilizers.

[0085] In some embodiments, the reaction of CaSO4 and CO2 includes two steps: (1) reaction of phosphogypsum with one or both of CO2+NH3 and NH4OH, and (2) catalytic decomposition of (NH4)2SO4 in the presence of a catalyst.

[0086] (1)CaSO4.2H2O+CO2+2NH3→CaCO3+(NH4)2SO4+H2O

[0087] (2) (NH4)2SO4→2NH3+H2SO4

[0088] In some cases, the catalyst can be an acid. In some cases, the acid catalyst can be sulfuric acid. Reaction (1) and / or reaction (2) can be carried out at ambient temperature or at -20°C, -19°C, -18°C, -17°C, -16°C, -15°C, -14°C, -13°C, -12°C, -11°C, -10°C, -9°C, -8°C, -7°C, -6°C, -5°C, -4°C, -3°C, -2°C, -1°C, 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, 11°C, 12°C, 13°C, 14°C, 15°C, 16°C, 17°C, 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, ℃、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℃、100℃、101℃、102℃、103℃、104℃、105℃、106℃、107℃、108℃、109℃、110℃、111℃、112℃、113℃、114℃、115℃、116℃、117℃、118℃、119℃、120℃、121℃、122℃ , 123°C, 124°C, 125°C, 126°C, 127°C, 128°C, 129°C, 130°C, 131°C, 132°C, 133°C, 134°C, 135°C, 136°C, 137°C, 138°C, 139°C, 140°C, 141°C, 142°C, 143°C, 144°C, 145°C, 146°C, 147°C, 148°C, 149°C, or 150°C, any temperature between the above temperatures, any temperature above the above temperatures, any temperature below the above temperatures, or any temperature within the above temperature range. In some cases, reaction (1) occurs at about 50°C to 70°C. Reaction (1) and / or reaction (2) can be reacted continuously or in batches. The reaction of reaction (1) and / or reaction (2) may last for 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes,17 minutes, 18 minutes, 19 minutes, 20 minutes, 21 minutes, 22 minutes, 23 minutes, 24 minutes, 25 minutes, 26 minutes, 27 minutes, 28 minutes, 29 minutes, 30 minutes, 31 minutes, 32 minutes, 33 minutes, 34 minutes, 35 minutes, 36 minutes, 37 minutes, 38 minutes, 39 minutes, 40 minutes, 41 minutes, 42 minutes, 43 minutes, 44 minutes, 45 minutes, 46 minutes, 47 minutes, 48 ​​minutes, 49 minutes, 50 minutes, 51 minutes, 52 minutes, 53 minutes, 54 minutes, 55 minutes, 56 minutes, 57 minutes, 58 minutes, 59 minutes, and / or 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, and / or 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, or the time between the above times, the time above the above times, the time below the above times, or the time within the range of the above times. Feed, reactants, products, etc. can be at 1 g / min, 2 g / min, 3 g / min, 4 g / min, 5 g / min, 6 g / min, 7 g / min, 8 g / min, 9 g / min, 10 g / min, 11 g / min, 12 g / min, 13 g / min, 14 g / min, 15 g / min, 16 g / min, 17 g / min, 18 g / min, 19 g / min, 20 g / min, 21g / min, 22g / min, 23g / min, 24g / min, 25g / min, 26g / min, 27g / min, 28g / min, 29g / min, 30g / min, 31g / min, 32g / min, 33g / min, 34g / min, 35g / min, 36g / min, 37g / min, 38g / min, 39g / min, 40g / min, 41g / min , 42g / min, 43g / min, 44g / min, 45g / min, 46g / min, 47g / min, 48g / min, 49g / min, 50g / min, 51g / min, 52g / min, 53g / min, 54g / min, 55g / min, 56g / min, 57g / min, 58g / min, 59g / min, 60g / min, 61g / min, 62g / min g / min, 63 g / min, 64 g / min, 65 g / min, 66 g / min, 67 g / min, 68 g / min, 69 g / min, 70 g / min, 71 g / min, 72 g / min, 73 g / min, 74 g / min, 75 g / min, 76 g / min, 77 g / min, 78 g / min, 79 g / min, 80 g / min, 81 g / min, 82 g / min,83 g / min, 84 g / min, 85 g / min, 86 g / min, 87 g / min, 88 g / min, 89 g / min, 90 g / min, 91 g / min, 92 g / min, 93 g / min, 94 g / min, 95 g / min, 96 g / min, 97 g / min, 98 g / min, 99 g / min, 100 g / min, 110 g / min, 120 g / min, 130 g / min, 140 g / min, 150 g / min, 160 g / min, 170 g / min, 180 g / min, 190 g / min, 200 g / min, 210 g / min, 220 g / min, 230 g / min, 240 g / min, 250 g / min, 260 g / min 0g / min, 270g / min, 280g / min, 290g / min, 300g / min, 310g / min, 320g / min, 330g / min, 340g / min, 350g / min, 360g / min, 370g / min, 380g / min, 390g / min, 400g / min, 410g / min, 420g / min, 430g / min, 440g / min, 450g / min, 460g / min, 470g / min, 480g / min, 490g / min, 500g / min, 510g / min, 520g / min, 530g / min, 540g / min, 550g / min, 560g / min, 570g / min / minute, 580 g / min, 590 g / min, 600 g / min, 610 g / min, 620 g / min, 630 g / min, 640 g / min, 650 g / min, 660 g / min, 670 g / min, 680 g / min, 690 g / min, 700 g / min, 710 g / min, 720 g / min, 730 g / min, 740 g / min, 750 g / min, 760 g / min, 770 g / min, 780 g / min, 790 g / min, 800 g / min, 810 g / min, 820 g / min, 830 g / min, 840 g / min, 850 g / min, 860 g / min, 870 g / min, 880 g / min 1000 g / min, 1500 g / min, 1600 g / min, 1700 g / min, 1800 g / min, 1900 g / min, 2000 g / min, 1000 g / min, 1500 g / min, 1600 g / min, 1700 g / min, 1800 g / min, 1900 g / min, 2000 g / min, 1000 g / min, 1500 g / min, 1600 g / min, 1700 g / min, 1800 g / min, 1900 g / min, 2000 g / min, 1000 g / min, 1500 g / min, 1600 g / min, 1700 g / min, 1800 g / min, 1900 g / min, 2000 g / min,21kg / min, 22kg / min, 23kg / min, 24kg / min, 25kg / min, 26kg / min, 27kg / min, 28kg / min, 29kg / min, 30kg / min, 31kg / min, 32kg / min, 33kg / min, 34kg / min, 35kg / min, 36kg / min, 37kg / min, 38kg / min, 39kg / min, 40kg / min, 41kg / min, 42kg / min, 43kg / min, 44kg / min, 45kg / min, 46kg / min, 47kg / min, 48kg / min, 49kg / min, 50kg / min, 51kg / min, 52kg / min kg / min, 53 kg / min, 54 kg / min, 55 kg / min, 56 kg / min, 57 kg / min, 58 kg / min, 59 kg / min, 60 kg / min, 61 kg / min, 62 kg / min, 63 kg / min, 64 kg / min, 65 kg / min, 66 kg / min, 67 kg / min, 68 kg / min, 69 kg / min, 70 kg / min, 71 kg / min, 72 kg / min, 73 kg / min, 74 kg / min, 75 kg / min, 76 kg / min, 77 kg / min, 78 kg / min, 79 kg / min, 80 kg / min, 81 kg / min, 82 kg / min, 83 kg / min, 84kg / min, 85kg / min, 86kg / min, 87kg / min, 88kg / min, 89kg / min, 90kg / min, 91kg / min, 92kg / min, 93kg / min, 94kg / min, 95kg / min, 96kg / min, 97kg / min, 98kg / min, 99kg / min, 100kg / min, 110kg / min, 120kg / min, 130kg / min, 140kg / min, 150kg / min, 160kg / min, 170kg / min, 180kg / min, 190kg / min, 200kg / min, 210kg / min, 220kg / min, 2 30kg / min, 240kg / min, 250kg / min, 260kg / min, 270kg / min, 280kg / min, 290kg / min, 300kg / min, 310kg / min, 320kg / min, 330kg / min, 340kg / min, 350kg / min, 360kg / min, 370kg / min, 380kg / min, 390kg / min, 400kg / min, 410kg / min, 420kg / min, 430kg / min, 440kg / min, 450kg / min, 460kg / min, 470kg / min, 480kg / min, 490kg / min, 500kg / min,510kg / min, 520kg / min, 530kg / min, 540kg / min, 550kg / min, 560kg / min, 570kg / min, 580kg / min, 590kg / min, 600kg / min, 610kg / min, 620kg / min, 630kg / min, 640kg / min, 650kg / min, 660kg / min, 670kg / min, 680kg / min, 690kg / min, 700kg / min, 710kg / min, 720kg / min, 730kg / min, 740kg / min, 750kg / min, 760kg / min, 770kg / min, 780kg / min, 790kg / min, 800kg / min, 810kg / min, 820kg / min, 830kg / min, 840kg / min, 850kg / min, 860kg / min, 870kg / min, 880kg / min, 890kg / min, 900kg / min, 910kg / min, 920kg / min, 930kg / min, 940kg / min, 950kg / min, 960kg / min, 970kg / min, 980kg / min, 990kg / min, 1000kg / min, 1 ton / min, 2 tons / min, 3 tons / min, 4 tons / min, 5 tons / min, 6 tons / min, 7 tons / min, 8 tons / min , 9 tons / minute, 10 tons / minute, 11 tons / minute, 12 tons / minute, 13 tons / minute, 14 tons / minute, 15 tons / minute, 16 tons / minute, 17 tons / minute, 18 tons / minute, 19 tons / minute, 20 tons / minute, 21 tons / minute, 22 tons / minute, 23 tons / minute, 24 tons / minute, 25 tons / minute, 26 tons / minute, 27 tons / minute, 28 tons / minute, 29 tons / minute, 30 tons / minute, 31 tons / minute, 32 tons / minute, 33 tons / minute, 34 tons / minute, 35 tons / minute, 36 tons / minute, 37 tons / minute, 38 tons / minute, 39 tons / minute, 40 tons / minute, 41 tons / minute, 42 tons / minute, 43 tons / minute, 44 tons / minute / minute, 45 tons / minute, 46 tons / minute, 47 tons / minute, 48 tons / minute, 49 tons / minute, 50 tons / minute, 51 tons / minute, 52 tons / minute, 53 tons / minute, 54 tons / minute, 55 tons / minute, 56 tons / minute, 57 tons / minute, 58 tons / minute, 59 tons / minute, 60 tons / minute, 61 tons / minute, 62 tons / minute, 63 tons / minute, 64 tons / minute, 65 tons / minute, 66 tons / minute, 67 tons / minute, 68 tons / minute, 69 tons / minute, 70 tons / minute, 71 tons / minute, 72 tons / minute, 73 tons / minute, 74 tons / minute, 75 tons / minute, 76 tons / minute, 77 tons / minute, 78 tons / minute, 79 tons / minute,80 tons / minute, 81 tons / minute, 82 tons / minute, 83 tons / minute, 84 tons / minute, 85 tons / minute, 86 tons / minute, 87 tons / minute, 88 tons / minute, 89 tons / minute, 90 tons / minute, 91 tons / minute, 92 tons / minute, 93 tons / minute, 94 tons / minute, 95 tons / minute, 96 tons / minute, 97 tons / minute, 98 tons / minute, 99 tons / minute, 100 tons / minute, 110 tons / minute, 120 tons / minute, 130 tons / minute, 140 tons / minute, 150 tons / minute, 160 tons / minute, 170 tons / minute, 180 tons / minute, 190 tons / minute, 200 tons / minute Tons / minute, 210 tons / minute, 220 tons / minute, 230 tons / minute, 240 tons / minute, 250 tons / minute, 260 tons / minute, 270 tons / minute, 280 tons / minute, 290 tons / minute, 300 tons / minute, 310 tons / minute, 320 tons / minute, 330 tons / minute, 340 tons / minute, 350 tons / minute, 360 tons / minute, 370 tons / minute, 380 tons / minute, 390 tons / minute, 400 tons / minute, 410 tons / minute, 420 tons / minute, 430 tons / minute, 440 tons / minute, 450 tons / minute, 460 tons / minute, 470 tons / minute, 480 tons / minute, 0 tons / minute, 490 tons / minute, 500 tons / minute, 510 tons / minute, 520 tons / minute, 530 tons / minute, 540 tons / minute, 550 tons / minute, 560 tons / minute, 570 tons / minute, 580 tons / minute, 590 tons / minute, 600 tons / minute, 610 tons / minute, 620 tons / minute, 630 tons / minute, 640 tons / minute, 650 tons / minute, 660 tons / minute, 670 tons / minute, 680 tons / minute, 690 tons / minute, 700 tons / minute, 710 tons / minute, 720 tons / minute, 730 tons / minute, 740 tons / minute, 750 tons / minute, 760 tons / minute Rates of 60, 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 tons / minute are conveyed or moved into, out of and / or through the system. Feeds, reactants, products, etc. can be at 0.1 bar, 0.2 bar, 0.3 bar, 0.4 bar, 0.5 bar, 0.6 bar, 0.7 bar, 0.8 bar, 0.9 bar, 1 bar, 2 bar, 3 bar, 4 bar, 5 bar, 6 bar, 7 bar, 8 bar, 9 bar, 10 bar, 11 bar, 12 bar, 13 bar, 14 bar,15 bar, 16 bar, 17 bar, 18 bar, 19 bar, 20 bar, 21 bar, 22 bar, 23 bar, 24 bar, 25 bar, 26 bar, 27 bar, 28 bar, 29 bar, 30 bar, 31 bar, 32 bar, 33 bar, 34 bar, 35 bar, 36 bar, 37 bar, 38 bar, 39 bar, 40 bar, 41 bar, 42 bar, 43 bar, 44 bar, 45 bar, 46 bar, 47 bar, 48 bar, 49 bar and / or 50 bar.

[0089] In some embodiments, the overall reaction can be described as the reaction of CaSO4 and CO2 to produce CaCO3, H2SO4, and water.

[0090] CaSO4.2H2O+CO2→CaCo3+H2SO4+H2O

[0091] Sulfuric acid can be recycled for use in phosphoric acid production.

[0092] Ca3(PO4)2+3H2SO4→3CaSO4+2H3PO4

[0093] In some embodiments, the overall reaction can be described as the reaction of Ca3(PO4)2, CO2, and water to form CaCO3, H3PO4.

[0094] Ca3(P04)2+3CO2+3H2O→3CaCO3+2H3PO4

[0095] See also Figure 1 , the disclosed embodiment flow chart demonstrates the simultaneous utilization of CO2 and CaSO4 to produce useful products, such as H2SO4, CaCO3, NH3, and H3PO4. The sulfuric acid is recycled back to phosphoric acid production, which eliminates or reduces the consumption of other H2SO4 resources. In some cases, calcium carbonate can be removed from the process and can be used as a starting material for other products, including fertilizers, and / or mixed with other compositions, including those that produce fertilizers.

[0096] See also Figure 2, describes a schematic diagram of a system and method for capturing carbon dioxide and utilizing calcium sulfate according to an example of the present invention. System 200 may include a first reactor 202 and a second reactor 204. A feed mixture 206 containing any raw material disclosed herein may be fed to the first reactor 202 alone or together. The first reactor 202 can have conditions suitable for the reaction described herein to produce one or more than one reaction product 208. All or a portion of the reaction product 208 may be transferred to the second reactor 204, separated (not shown), and / or removed from the system (not shown). The second reactor may have conditions suitable for the reaction described herein to produce a reaction product 210. In some cases, the second reactor receives additional reactant products, or reactant products different from those appearing in 206 and suitable for the reaction described herein (not shown). All or a portion of the reaction product 210 may be transferred to the first reactor 202 (not shown), transferred to the second reactor 204 (not shown), separated (not shown) and / or removed from the system. In some cases, the feed mixture 206 may contain calcium sulfate, carbon dioxide, ammonia and / or ammonium hydroxide, calcium phosphate and / or sulfuric acid. Reaction product 208 may include calcium sulfate, carbon dioxide, ammonia and / or ammonium hydroxide, phosphoric acid, calcium carbonate and / or ammonium sulfate. Reaction product 210 may include calcium sulfate, carbon dioxide, ammonia, ammonium hydroxide, calcium carbonate, ammonium sulfate, phosphoric acid and / or sulfuric acid.

[0097] See also Figure 3, describes a schematic diagram of a system and method for capturing carbon dioxide and / or utilizing calcium sulfate according to another example of the present invention. System 300 may include a first reactor 302, a second reactor 304, and a third reactor 306. A feed mixture component 308, which may include calcium phosphate and sulfuric acid, may be added to the first reactor 302 alone or in combination. All or a portion of the feed mixture 308 may react in the first reactor 302 to produce a reaction product, which may include calcium sulfate and / or phosphoric acid. In some cases, phosphoric acid 319 may be separated from calcium sulfate. In some cases, the separation occurs in a separator (not shown). Mixture 310 may include reaction products and / or calcium sulfate, which have been at least partially purified by removing at least some of the phosphoric acid. Reactant stream 320 may include carbon dioxide, optionally one or more than one of ammonia and ammonium hydroxide, and may be transported to the second reactor 304 together with all or a portion of mixture 310. All or a portion of mixture 310 may react in the second reactor 304 to produce a second reaction product, which may include calcium carbonate and ammonium sulfate. In some cases, calcium carbonate 321 can be separated from ammonium sulfate. In some cases, calcium carbonate is not separated from ammonium sulfate. In some cases, the separation occurs in a separator, such as a second separator (not shown). Mixture 312 can include a second reaction product or ammonium sulfate, which has been at least partially purified by removing at least a portion of calcium carbonate. Catalyst stream 322 can include a catalyst, such as an acid, which can be sulfuric acid, which can be optionally transported to third reactor 306 with all or part of mixture 312. All or part of mixture 312 can be catalytically decomposed in third reactor 306 to produce sulfuric acid composition 316 and ammonia composition 318 or a mixture 314 of the two. All or part of sulfuric acid composition 316 can be combined with feed mixture 308. All or part of ammonia composition 318 can be combined with mixture 310. All or part of mixture 314 can be removed from the system. All or part of sulfuric acid composition 316 can be removed from the system (not shown). All or part of ammonia composition 318 can be removed from the system (not shown).

[0098] III. How to use fertilizer

[0099] Fertilizers of the present disclosure, including fertilizer granules, compositions comprising the fertilizers, and fertilizer mixtures comprising the fertilizers, can be used in methods for increasing the amount of one or more plant nutrients in soil and promoting plant growth. This method can include applying an effective amount of a composition and / or mixture containing the fertilizer of the present invention to the soil. The method can include increasing the growth and yield of crops, trees, ornamental plants, etc. For example, palm, coconut, rice, wheat, corn, barley, oats, and / or soybeans. The method can include applying the fertilizer mixture of the present invention to at least one of soil, organisms, liquid carriers, liquid solvents, etc. One or more compositions and / or one or more fertilizer mixtures containing fertilizers can be applied to plants and / or soil as topdressing, base fertilizer, and / or by any suitable application method.

[0100] Non-limiting examples of plants that can benefit from the fertilizer of the present invention include lianas, trees, shrubs, stem plants, ferns, etc. Plants can include orchard crops, lianas, ornamental plants, food crops, timber, and harvested plants. Plants can include gymnosperms, angiosperms, and / or ferns.

[0101] The effectiveness of a composition comprising a fertilizer of the present invention can be determined by measuring the amount of calcium and optionally other nutrients in the soil at different times after the fertilizer composition is applied to the soil. It is understood that different soils have different properties that can affect the stability of nutrients in the soil. The effectiveness of a fertilizer composition can also be directly compared to other fertilizer compositions by making a side-by-side comparison in the same soil under the same conditions.

[0102] Example

[0103] The present invention will be described in more detail by way of specific examples. The following examples are provided only for illustrative purposes and are not intended to limit the present invention in any way. Those skilled in the art will easily recognize various noncritical parameters that can be varied or changed to produce substantially the same results.

[0104] Example 1

[0105] 50g of CaSO4.2H2O can be loaded into the Parr reactor to react with CO2 and NH3 gases introduced through the Parr reactor at a flow rate of 25cc / min. The reactor interior can be heated to 60°C and the pressure inside the reactor can be at least 25 bar. The reaction can last for 2 hours and then the reactor is cooled to room temperature. The reaction can form a product in the form of a suspension. The suspension can be filtered to separate CaCO3 and (NH4)2SO4. The liquid containing the (NH4)2SO4 filtrate can be dried at 120°C for 8 hours. 43g of the dried product containing (NH4)2SO4 can react with a decomposition catalyst of 5g 60% sulfuric acid in a U-shaped quartz reactor. The reactor can be heated to 45°C to decompose ammonium sulfate. The ammonia produced can be discharged from the reaction by ventilation. After 1 hour, the reactor can be cooled to collect the remaining sulfuric acid catalyst and the produced sulfuric acid.

[0106] ***

[0107] All methods disclosed and claimed herein can be implemented and performed according to the present disclosure and without undue experimentation. Although the compositions and methods of the present invention have been described according to preferred embodiments, it is obvious to those skilled in the art that the steps or sequence of steps of the methods and methods described herein can be changed without departing from the concept, spirit and scope of the present invention. More specifically, it is obvious that certain reagents related in both chemical and physiological aspects can replace the reagents described herein while achieving the same or similar results. All such similar substitutions and changes that are obvious to those skilled in the art are considered to be within the spirit, scope and concept of the present invention as defined by the appended claims.

Claims

1. A method for capturing CO2 and using calcium sulfate (CaSO4) to produce sulfuric acid (H2SO4), the method comprising the following steps: (a) contacting calcium sulfate (CaSO4) with carbon dioxide (CO2), and one or both of ammonia (NH3) and ammonium hydroxide (NH4OH) to produce a first product comprising calcium carbonate (CaCO3) and ammonium sulfate ((NH4)2SO4); and (b) decomposing (NH4)2SO4 in the first product into NH3 and sulfuric acid (H2SO4) by contacting (NH4)2SO4 with a catalyst.

2. The method according to claim 1, further comprising: (c) contacting the H2SO4 produced in step (b) with calcium phosphate (Ca3(PO4)2) to produce phosphoric acid (H3PO4) and CaSO4.

3. The process according to claim 1 or 2, wherein the catalyst is an additional acid, preferably H2SO4.

4. The method according to any one of claims 1 to 3, wherein: The source of CaSO4 in step (a) includes waste gypsum and / or recycled gypsum; the source of CO2 in step (a) includes waste gas and / or flue gas from industrial facilities; and / or The source of CaSO4 in step (a) includes phosphogypsum.

5. The method according to any one of claims 1 to 4, wherein step (a) is performed at about 50°C to 70°C.

6. The method according to any one of claims 1 to 5, further comprising separating CaCO3 from the first product before step (b).

7. The method according to claim 6, further comprising: Drying the separated CaCO3; and / or The separated CaCO3 is combined with plant nutrients to form a fertilizer.

8. The method according to any one of claims 1 to 7, wherein: using at least a portion of the NH3 generated in step (b) as at least a portion of the NH3 used in step (a); using at least a portion of the H2SO4 generated in step (b) as at least a portion of the H2SO4 for generating phosphogypsum; and / or At least a portion of the generated phosphogypsum is used as a source of CaSO4 in step (a).

9. A system for capturing CO2 and using calcium sulfate (CaSO4) to produce sulfuric acid (H2SO4), the system comprising: (a) a first reactor capable of receiving CaSO4, CO2, and one or both of NH3 and NH4OH and providing conditions to produce a product comprising CaCO3 and (NH4)2SO4; (b) a second reactor capable of decomposing the (NH4)2SO4 produced from reactor (a) into H2SO4 and NH3; and (c) optional means capable of separating CaCO3 from the product produced in the first reactor.

10. The system of claim 9, wherein the first reactor and the second reactor are the same reactor.

11. The system of claim 9, wherein the first reactor and the second reactor are different reactors, and the system further comprises means for connecting the first reactor and the second reactor.

12. The system of any one of claims 9 to 11, further comprising a third reactor capable of receiving H2SO4 and calcium phosphate (Ca3(PO4)2) and providing conditions to produce CaSO4 and phosphoric acid (H3PO4).

13. The system of claim 12, wherein: The third reactor and the second reactor are the same reactor; and / or The third reactor, the second reactor and the first reactor are the same reactor.

14. The system of any one of claims 12 to 13, wherein the third reactor, the second reactor, and the first reactor are different reactors.

15. The system according to any one of claims 9 to 14, wherein the first reactor is capable of receiving and reacting CO2 from flue gas and / or waste gas of an industrial facility, preferably wherein the CO2 from the flue gas and / or waste gas is not purified to separate or concentrate the CO2 in the flue gas and / or waste gas before reacting to form CaCO3.

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