POLLUTED CO2 CAPTURING WITH LIME PRODUCED FROM PHOSPHOGYPSUM CALCINATION USING SULFUR AS NON-CO2 FUEL TECHNICAL FIELD The present invention relates to capturing polluted CO ₂ with CaO produced from phosphogypsum calcination using sulfur as non-CO2 Fuel. BACKGROUND OF THE INVENTION [0001] Significant quantities of phosphogypsum and carbon dioxide (CO2) waste are produced every year. Phosphogypsum (PG) disposal represents a special challenge, requiring significant investments to prepare new containment area every 5 to 7 years of operations and limiting the expansion of phosphoric acid production due to limitation in gypsum disposal areas. In addition, high calcium content in the phosphate concentrate requires higher consumption of sulfuric acid (SA), which increases sulfur consumption and costs. [0002] Ammonia operations expansion also presents challenges by increasing CO2 emissions with potential penalties and potential downgrading of products due to being non-green and by missing the increasing market opportunity to supply blue ammonia or low CO2 ammonia. CO2 production can be divided in two categories: clean CO ₂ , which is suitable for use in products like urea and methanol, and polluted CO ₂ , from combustion exhaust gases or phosphoric acid production of acidic fumes, which are not suitable for use as is. [0003] Traditional technologies have approached the phosphogypsum thermal treatment to produce various building materials including: (1) neutralization with lime (CaO) and drying then it is added to clinker and milled together to produce Portland cement; (2) pre-calcination of phosphogypsum to produce alfa hemi-hydrate gypsum (α-HH); and (3) the use of washed/treated phosphogypsum as source of CaO in the raw meal with carbon, silica and ferrous to produce clinker in extended drying, calcination and clinkering in an energy intensive extended kiln plants. It is noted that the energy consumption to produce clinker in this method can consume up to 200% of the energy consumed in traditional clinker production process from limestone. [0004] Traditional key technologies related to calcination of phosphogypsum and formation of limestone, typically include: (1) energy intensive phosphogypsum calcination into calcium oxide (CaO) and sulfur dioxide (SO ₂ ), which is well known in the previous art [1, 2]; (2) sulfuric acid production from SO ₂ rich gases, which is well established in applications including zinc, copper, and iron smelters' exhaust gases treatment, as well as the exhaust gases treatment from phosphogypsum calcination. However, the use of sulfur or sulfur-rich fuel in the calcination is considered a disadvantage because of higher concentration of SO2 in exhaust gases due to excessive quantities of SA that is produced. [0005] Traditional key technologies related to CO ₂ capturing and storage or utilization, typically include: (1) capturing and injection to enhance oil recovery, in place of steam or water injection in old wells; (2) purification and consumption in the production of chemicals like methanol, urea and polymers; (3) injection into microalgae reservoir as a source of CO ₂ for photosynthesis to increase their growth; (4) purification for use a food grade CO2 in beverages and dry-ice applications; (5) CO2 capturing with CaO in flue gases to produce byproduct limestone (LS) as exemplified in ref. [3] and Pat. No. CA2773080. An extended description of the Circular Fluid-Bed reactor (CFB) to capture CO ₂ with CaO is exemplified in ref. [1]. [0006] The problem with producing CaO is usually associated with limestone (CaCO ₃ ) calcination with hydrocarbon fuel, which generates approximately 200% excess CO2 from both fuel and CaCO3, compared to the amount of CO2 that would be captured by CaO. [0007] The use of hydrocarbon fuel to calcine phosphogypsum also generates significant quantity of CO ₂ that cannot justify the reuse of CaO produced for CO2 capturing. [0008] The foregoing issues signal the need for a method that overcomes the limitations of traditional processes and avoids restrictions in applicability to multiple raw material, while reducing materials waste and providing cost advantages with a net reduction of CO2 emissions.

SUMMARY OF THE EMBODIMENTS [0009] In certain embodiments, the present invention provides an alternative integrated method to utilize the main waste streams from phosphate and ammonia operations, comprising phosphogypsum and CO ₂ to both reduce their footprint and to produce commercial products. [0010] In one aspect, the invention is directed at a novel integrated process that captures the CO2 produced from ammonia and phosphate processing operations, comprising hydrocarbon fuels (HC) combustion and calcareous phosphate rock digestion in a phosphoric acid plant (PAP), with acidic fumes and CO2 emissions. The recycled CO ₂ is then captured by CaO produced from phosphogypsum calcination to obtain limestone, with significant heat recovery from the reaction of CO2 and CaO. This novel approach allows converting calcium from phosphate rock (PR), currently disposed as waste phosphogypsum, to useful building material like limestone. [0011] In certain embodiments, disclosed herein is a method featuring capturing high CO2 acidic off-gases produced in the digestion of low-grade calcareous phosphate ore with sulfuric acid (SA) in the known wet phosphoric acid process (WPA) to produce phosphoric acid and phosphogypsum. [0012] The integrated process disclosed herein is both unique and novel in nature that reduces the waste CO ₂ and phosphogypsum and provides cost advantages by: [0013] (1) using CaO from the PG to capture CO2 and fix it in CaCO3 form on a permanent basis, [0014] (2) reducing the consumption of sulfur by the sulfuric acid regeneration from phosphogypsum and reduce the accumulation of waste PG during the phosphate processing to produce phosphoric acid from phosphate rock, [0015] (3) reducing the consumption of hydrocarbon fuel in the calcination of phosphogypsum. [0016] (4) allowing net reduction of CO2 emission from phosphate and ammonia operations and avoiding penalties related to CO ₂ emissions. BRIEF DESCRIPTION OF THE FIGURES [0017] The invention can be better understood with reference to the following figure and description. [0018] FIG.1 illustrates the method for capturing polluted CO2 with CaO produced from phosphogypsum calcination using sulfur as non-CO2 fuel as a block diagram.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS [0020] The present invention provides an integrated method to capture CO ₂ with CaO produced from phosphogypsum calcination using sulfur as non-CO2 fuel. [0021] In certain embodiments exhaust gases are flown in counter current to a PG calcination plant (block B) and from the phosphogypsum calcination plant to a drying plant (block A), where phosphogypsum is initially fed from dry stack at a moisture level of 10-40%. [0022] In a preferred embodiment, the phosphogypsum from dry stack is fed at a moisture level of 20- 30%. [0023] In certain embodiments, the counter current flow of gases and solids comprises the following steps: (1) sulfur burning; (2) phosphogypsum calcination; (3) phosphogypsum pre-calcination; and (4) phosphogypsum drying. [0024] In one embodiment, sulfur burning: S + O ₂ = SO ₂ is conducted at an approximate temperature range of approximately 1100-1400°C. [0025] In a preferred embodiment, sulfur burning, is conducted at an approximate temperature range of l200-1300°C [0026] In another embodiment, (2) heat is applied at an approximate temperature range of 1100-1500°C for phosphogypsum (CaSO ₄ ) calcination. [0027] In a preferred embodiment, heat is applied at an approximate temperature range of 1200-1400°C for phosphogypsum (CaSO4) calcination. [0028] In one embodiment, pre-calcination of phosphogypsum, is described by the following reaction: CaSO4.2H2O + heat = CaSO4 + 2H2O(v); where heat is applied at an approximate temperature range of 600-1000°C; [0029] In a preferred embodiment, heat is applied at an approximate temperature range of 700-900°C to reaction pre-calcination of phosphogypsum. [0030] In one embodiment, (4) drying of fee moisture, is described as follows: H ₂ O(1) + heat = H ₂ O(v); where heat is applied at an approximate temperature range of 300-700°C; [0031] In a preferred embodiment, heat is applied at an approximate temperature range of 400-600°C to dry the fee moisture. [0032] In one embodiment, temperature of gases must be controlled above 300°C to avoid condensation produced in steps (1) to (4), where excess SO ₂ is reacted with H ₂ O to obtain H ₂ SO ₃ , as described by the following reaction: SO2 + H2O = H2SO3 at an approximate temperature of less than 250°C. [0033] In certain embodiments, SO2-rich stream produced from drying phosphogypsum in block A is partially washed with Ca(OH) ₂ solution to treat the waste gas stream as described by the following reactions: 2Ca(OH)2 + 2SO2 + O2 = 2CaSO4 + H2O + heat, and Ca(OH)2 + 2CO = CaCO3 + C + H2O + heat. The waste gas stream is then cooled to less than 450°C in block D, before feeding SO ₂ to a waste gas sulfuric acid plant (WG-SAP) in block E. [0034] In a preferred embodiment, the waste gas stream described above is then cooled to an approximate temperature range of 350 to 400°C in block D, before feeding SO ₂ to a waste gas sulfuric acid plant (WG- SAP) in block E. [0035] In certain embodiments, sulfur utilized as the main source of fuel with air and a carbon source used as reducing agent, for phosphogypsum calcination in block B, and the decomposed phosphogypsum SO2, together generate a gas stream at an approximate concentration range of 16-20% SO2 by weight. This concentration is similar to the SO2 concentration produced by direct sulfur burning in conventional sulfuric acid plant (SAP), where this high concentration stream is diluted to approximately concentration of 10-12% before feeding to an SO2/SO3 converter operating according to reactions: 2SO ₂ + O ₂ = 2SO ₃ + heat; where temperature is controlled at an approximate range of 400-450°C; then sulfuric acid is produced by SO3 absorption with water according to reaction: SO3 + H2O = H2SO4 + heat; where temperature is controlled at an approximate range of 80-160°C. [0036] In a preferred embodiment, the SO2-rich gas stream has an approximate concentration range of 13-25% SO2 by weight. [0037] In a preferred embodiment, the reaction 2SO ₂ + O ₂ = 2SO ₃ + heat is controlled at an approximate temperature range of 350 to 500°C. [0038] In a preferred embodiment, the reaction SO ₃ + H ₂ O = H ₂ SO ₄ + heat is controlled at an approximate temperature range of 75 to 165°C. [0039] In certain embodiments, conventional SAP can use the SO2 gas stream coming from described phosphogypsum calcination with sulfur as fuel. In contrast, where conventional hydrocarbon fuel is used to calcine the phosphogypsum, the SO2 concentration that is produced is below 10%, which can impact significantly the capacity of the existing SAP as well as the concentration of product sulfuric acid . [0040] In certain embodiments, concentrated sulfuric acid produced in the waste gas sulfuric acid plant is utilized for digesting phosphate rock to obtain phosphoric acid and byproduct phosphogypsum. [0041] In certain embodiments, byproduct phosphogypsum can be used directly or stacked for drying prior to feeding to block A. [0042] In certain embodiments, CaO powder produced in the calcination plant is reacted with CO ₂ in a circular fluid bed reactor to obtain CaCO3, according to the reaction: CaO + CO2 = CaCO3 + heat; where reaction is applied at a temperature below approximately 650°C. [0043] In a preferred embodiment, reaction CaO + CO ₂ = CaCO ₃ + heat is controlled at an approximate temperature below 600°C. [0044] In a most preferred embodiment, reaction CaO + CO ₂ = CaCO ₃ + heat is controlled at an approximate temperature below 400°C. [0045] In certain embodiments, CO ₂ utilized in the circular fluid bed reactor is produced from acidic fumes from a source selected from the group consisting of a phosphoric acid plant, hydrocarbon fuel combustion, and hydrogen reformers. [0046] In certain embodiments, CaO powder is utilized to precipitate acid fumes from phosphogypsum calcination, as described in reactions (x), (xi), and (xii): (x) CaO + H ₃ PO ₄ = CaHPO ₄ + H ₂ O; (xi) CaO + 2HF = CaF ₂ + H ₂ O; (xii) CaO + H2SiF6 = CaSiF6 + H2O.

[0047] Material and Methods [0048] A method is disclosed, with reference to FIG.1, where polluted CO ₂ is captured with CaO that is produced from phosphogypsum calcination using sulfur as a non-CO2 fuel. [0049] The method comprises the following operations: [0050] PG from dry stack, normally at moisture level of 15-30%, is fed for drying in block A and calcination in block B in counter-current to sulfur fuel and exhaust gases to achieve better energy recovery and reduce the temperature of the exhaust SO ₂ -rich stream. Counter current flow of gases and solids follow the sequence: (1) sulfur burning, (2) phosphogypsum calcination, (3) phosphogypsum pre-calcination and (4) phosphogypsum drying. Described herein are the corresponding reactions: 1. Sulfur Burning: S + O ₂ = SO ₂ (T=1200-1300°C); 2. CaSO4 calcination: 2CaSO4 + C + heat = 2CaO + 2SO2 + CO2 (T=1100-1300°C); 3. Pre-calcination of PG: CaSO ₄ .2H ₂ O + heat = CaSO ₄ + 2H ₂ O(v) (T=700-900°C); 4. Drying of Fee moisture: H2O(1) +heat = H2O(v) (T=400-600°C). [0051] Crystalline and free water are removed in reactions (3) and (4) respectively. [0052] Removal of crystalline and free water in reactions (3) and (4) respectively, is utilized for cooling the SO ₂ flue gases below approximately 700°C. [0053] Moreover, gases temperature must be maintained above 300°C to avoid SO2 condensation, where SO2 is reacted with H2O to produce H2SO3 as described by the following reaction: [0054] 5. SO ₂ + H ₂ O = H ₂ SO ₃ (1) (T<250°C). [0055] SO2-rich stream after drying the PG in (block A), is partially treated and further cooled in block D, using milk of lime (Ca(OH) ₂ ) washing prior to feeding to waste gas sulfuric acid plant (WG-SAP) in block E, as exemplified by the following reactions: [0056] 6.2Ca(OH)2 + 2SO2 + O2 = 2CaSO4 + H2O + heat; [0057] 7. Ca(OH) ₂ + 2CO = CaCO ₃ + C + H ₂ O + heat. [0058] The use of sulfur (S) as main fuel in block B, together with a C-source as reducing agent, allows the SO ₂ -rich gas to be highly concentrated in SO ₂ , in the range of 16-20%, comparable to conventional SAP based on burning S. This reaction allows the direct implementation on existing SAP plants prior to the SO2 to SO3 conversion stage, which operates at SO2 concentrations above 10-12%, as described herein: [0059] 8.2SO ₂ + O ₂ = 2SO ₃ +Heat (T=400-450°C); [0060] 9. SO3 + CO2 + H2O = H2SO4 + CO2 + Heat (T=80-160°C). [0061] SA produced from WG-SAP in block E is usually used to digest phosphate rock (PR) and produce Phosphoric Acid (PA) and byproduct phosphogypsum that is stacked and re-introduced to block A. This step allows to minimize the amount of phosphogypsum build up in phosphate operations. [0062] CaO powder from block B is sent to a Circular Fluid Bed Reactor (CFBR) in block C where CaO is reacted with CO2 produced by other sources, comprising: acidic fumes with CO2 from PAP, hydrocarbon fuel combustion CO ₂ , and pure CO ₂ from hydrogen reformers. Solid limestone (LS) is produced in powder form containing some of the impurities coming originally from the PG, as described by the following reaction: [0063] 10. CaO + CO ₂ = CaCO ₃ + Heat (T<600°C). [0064] CaO powder attacks remaining acids fumes coming from phosphogypsum calcination and captures CO ₂ stream from PAP operations with all other harmful fumes, as described by the following reactions: [0065] 11. CaO + H3PO4 = CaHPO4 + H2O; [0066] 12. CaO + 2HF = CaF2 + H2O; [0067] 13. CaO + H ₂ SiF ₆ = CaSiF ₆ + H ₂ O. [0068] The present invention proposes an integrated method to achieve the following key advantages: (i) utilizing recycled phosphogypsum and avoiding the large-scale phosphogypsum stacks that are known environmental concern in the phosphate processing industry; (ii) using calcium from phosphate ores to capture CO2 emitted from different sources of CO2. This is achieved by converting the calcium in phosphate to phosphogypsum and then to lime, which is then used to capture CO ₂ , which in-turn produces LS, a known safe building material; (iii) increasing the SA production linked to the production of phosphoric acid (PA) from phosphate rock digestion with SA that produces phosphogypsum, which is in turn calcined with S as fuel. Excess SA production can be utilized to increase PA production or the production of other SA derivatives; (iv) reducing the need for equivalent hydrocarbon fuel source to conduct the PG calcination by using S as fuel, thereby reducing the total S required to for SA production. The total consumption of sulfur in SAP production is reduced to 50-60% of conventional SAP based on sulfur burning alone; (v) capturing of acidic fumes (AF) in various forms produced in PAP operations by utilizing CaO, a known sorbent for various acidic fumes, comprising: (AF) like; hydrofluoric acid (HF), hydroiodic acid (HI), fluorosilicic acid (FSA) as well as CO2, to make; calcium fluoride (CaF2), calcium iodate (CaI ₂ ), and calcium hexafluorosilicate (CaSiF ₆ ), respectively; (vi) neutralizing various acids derived from phosphogypsum processing with CaO, including, for example: SA, PA, and FSA in stable form, to obtain CaSO4, dicalcium phosphate (CaHPO4) and calcium fluosilicate (CaSiF6), respectively. LS and the calcium compounds described above are considered stable and environmentally friendly; (vii) generating energy in excess of that produced by the integrated method of the present invention by using sulfur as a fuel to calcine the phosphogypsum and produce SA and capture CO ₂ in limestone: (1) 75% of energy recovered sulfur burning in conventional SAP; (2) when phosphogypsum is used to produce clinker, using sulfur as fuel to calcine phosphogypsum to CaO saves 40-50% of the total energy required to produce clinker from phosphogypsum when only hydrocarbon fuels are used. On the other hand, using sulfur as fuel will reduce clinker production’s net CO2 emissions by 75%, compared to conventional limestone-based clinker plants. [0069] As used herein, the term “phosphogypsum” is defined to mean is a by-product from the production of phosphoric acid by treating phosphate ore with sulfuric acid and producing gypsum (CaSO4·2H2O). [0070] As used herein, the term “precipitating acid fumes” refers to reacting acidic components in fumes with a base, thereby trapping the acid in the form of a salt. [0071] Prophetic example [0072] Most of the technology identified and utilized by the new integrated process concept in this invention are well proven and have been demonstrated commercially. [0073] Sulfur use as fuel in the calcination of phosphogypsum is not recognized in previous arts and is considered a key novelty of the present invention. On the other hand, gypsum calcination with other fuels is well demonstrated [1]. Also, the burning of sulfur for SAP plants is well established on large scale. [0074] CO ₂ capturing by CaO in a circular fluid bed reactor (CFBR) is required to be scaled up for large application as we are evaluating to use in the integrated concept in this invention [4, 5]. [0075] To demonstrate the total energy and mass balance for the integrated concept in this invention (A) versus; (B) conventional SA production from sulfur burning and (C) the use of methane as fuel for phosphogypsum calcination, (D) the calcination of limestone to produce lime (in clinker’s preheater and calcination), the following table summarize the Ins and Outs for two case studies: Case Sulfur CH ₄ PG CO ₂ LS SA Net Heat [0076] the use of hydrocarbon fuel will reduce the amount of net CO2 that can be captured from other sources by 50%, compared to the use of sulfur as fuel. [0077] the use of sulfur as fuel to caline phosphogypsum increases the sulfuric acid production and reduces the specific consumption of sulfur to produce sulfuric acid by 40-50% compared to conventional SAP operations based on only sulfur burning. [0078] heat recovery with the use of sulfur as fuel and CO2 capturing is estimated to recover 70-80% of the energy compared to the energy recovered in convention SAP operations based on only sulfur burning. [0079] CaO produced from phosphogypsum calcination with sulfur as fuel will reduce the CO2 emission by 70- 80% compared to the use of limestone and hydrocarbon fuel for producing CaO in conventional clinker plant. [0080] References [0081] [1] Reductive Decomposition of Gypsum by Carbon Monoxide, Thomas D. Wheelock, D.R. Boylan, Chemical and Biological Engineering Publications, Iowa State University, 960. [0082] [2] Decomposition of Calcium Sulfate: A Review of Literature, W.M. Swift, A.F. Panek, G.W. Smith, G.J. Vogel and A. A. Jonke, Chemical Engineering Division, Argonne National Laboratory, Illinois, USA. [0083] [3] Effect of Temperature on the Carbonation Reaction of CaO with CO2 Zhen-shan Li, Fan Fang, Xiao-yu Tang, and Ning-sheng Cai, ACS publication, dx.doi.org/10.1021/ef201543n, Energy Fuels 2012, 26, 2473-2482. [0084] [4] Experimental investigation of a circulating fluidized-bed reactor to capture CO2 with CaO, N. Rodriguez, M. Alonso,J. C. Abanades, Environmental and Energy Engineering, First published: 12 April 2011, https://doi.org/10.1002/aic.l2337. [0085] [5] Experimental research and modeling of multiple carbonation/calcination cycle of Ca-based CO2 sorbents. Research gate, May 2009, F. Fang, Z.-S. Li, NingshengCai.