WO2022245733A4 - Systems and methods to recover value-added materials from gypsum - Google Patents
Systems and methods to recover value-added materials from gypsum Download PDFInfo
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- WO2022245733A4 WO2022245733A4 PCT/US2022/029451 US2022029451W WO2022245733A4 WO 2022245733 A4 WO2022245733 A4 WO 2022245733A4 US 2022029451 W US2022029451 W US 2022029451W WO 2022245733 A4 WO2022245733 A4 WO 2022245733A4
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- WO
- WIPO (PCT)
- Prior art keywords
- filtrate
- impurities
- calcium
- metal
- carbonate
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract 8
- 229910052602 gypsum Inorganic materials 0.000 title abstract 4
- 239000010440 gypsum Substances 0.000 title abstract 4
- 239000000463 material Substances 0.000 title 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract 45
- 239000012535 impurity Substances 0.000 claims abstract 44
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract 23
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract 23
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract 23
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract 22
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract 14
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract 10
- 239000001099 ammonium carbonate Substances 0.000 claims abstract 10
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract 9
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims abstract 6
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims abstract 5
- 229910052776 Thorium Inorganic materials 0.000 claims abstract 5
- 229910052770 Uranium Inorganic materials 0.000 claims abstract 5
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract 2
- 239000000706 filtrate Substances 0.000 claims 80
- 229910052751 metal Inorganic materials 0.000 claims 36
- 239000002184 metal Substances 0.000 claims 36
- 239000002002 slurry Substances 0.000 claims 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 14
- 229910052791 calcium Inorganic materials 0.000 claims 14
- 239000011575 calcium Substances 0.000 claims 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 6
- 239000013078 crystal Substances 0.000 claims 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 5
- 239000001569 carbon dioxide Substances 0.000 claims 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 5
- 229910052749 magnesium Inorganic materials 0.000 claims 5
- 239000011777 magnesium Substances 0.000 claims 5
- 239000002904 solvent Substances 0.000 claims 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 4
- 229910052782 aluminium Inorganic materials 0.000 claims 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 4
- 159000000007 calcium salts Chemical class 0.000 claims 4
- 229910052684 Cerium Inorganic materials 0.000 claims 3
- 229910052779 Neodymium Inorganic materials 0.000 claims 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 3
- 229910052742 iron Inorganic materials 0.000 claims 3
- 229910052746 lanthanum Inorganic materials 0.000 claims 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims 3
- 229910052727 yttrium Inorganic materials 0.000 claims 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 2
- 239000000908 ammonium hydroxide Substances 0.000 claims 2
- 229910052788 barium Inorganic materials 0.000 claims 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 2
- 239000000920 calcium hydroxide Substances 0.000 claims 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- 229910052712 strontium Inorganic materials 0.000 claims 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims 1
- 239000004254 Ammonium phosphate Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 claims 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims 1
- 235000019289 ammonium phosphates Nutrition 0.000 claims 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims 1
- 239000000347 magnesium hydroxide Substances 0.000 claims 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims 1
- 229910052863 mullite Inorganic materials 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 239000001103 potassium chloride Substances 0.000 claims 1
- 235000011164 potassium chloride Nutrition 0.000 claims 1
- 229910000160 potassium phosphate Inorganic materials 0.000 claims 1
- 235000011009 potassium phosphates Nutrition 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000002893 slag Substances 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- 235000011008 sodium phosphates Nutrition 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 229910000018 strontium carbonate Inorganic materials 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract 2
- 239000000047 product Substances 0.000 abstract 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 abstract 1
- 235000010261 calcium sulphite Nutrition 0.000 abstract 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 abstract 1
- 238000006477 desulfuration reaction Methods 0.000 abstract 1
- 230000023556 desulfurization Effects 0.000 abstract 1
- 239000003546 flue gas Substances 0.000 abstract 1
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract 1
- 150000004692 metal hydroxides Chemical class 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000002285 radioactive effect Effects 0.000 abstract 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D36/00—Filter circuits or combinations of filters with other separating devices
- B01D36/04—Combinations of filters with settling tanks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0488—Flow sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0018—Evaporation of components of the mixture to be separated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0018—Evaporation of components of the mixture to be separated
- B01D9/0027—Evaporation of components of the mixture to be separated by means of conveying fluid, e.g. spray-crystallisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0036—Crystallisation on to a bed of product crystals; Seeding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/005—Selection of auxiliary, e.g. for control of crystallisation nuclei, of crystal growth, of adherence to walls; Arrangements for introduction thereof
- B01D9/0054—Use of anti-solvent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0059—General arrangements of crystallisation plant, e.g. flow sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0063—Control or regulation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/07—Preparation from the hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Disclosed herein are systems and methods from processing flue gas desulfurization (FGD) gypsum feedstock and ash feedstocks, either separately or together. FGD gypsum conversion comprises reacting FGD gypsum (calcium sulfate) feedstock or phosphogypsum, in either batch or continuous mode, with ammonium carbonate reagent to produce commercial products comprising ammonium sulfate and calcium carbonate. A process to separate the impurities and convert the calcium carbonate to a pure precipitated calcium carbonate is disclosed. These impurities include a concentrate of valuable Rare Earth Elements, and radioactive thorium and uranium. A process to convert calcium sulfite to calcium sulfate using oxygen and a catalyst is also disclosed. Ash conversion comprises a leach process followed by a sequential precipitation process to selectively precipitate products at predetermined pHs resulting in metal hydroxides which may be converted to oxides or carbonates. The processes may be controlled by use of one or more processors.
Claims
1. A system comprising: a phosphogypsum feedstock comprising calcium sulfate and at least two impurities; a mixer to combine ammonia gas, carbon dioxide, and water, resulting in an ammonium carbonate reagent solution; one or more first reactors to combine and react the phosphogypsum feedstock with the ammonium carbonate reagent solution, resulting in a first reacted slurry, comprising calcium carbonate, ammonium sulfate, and the at least two impurities; a first filter to separate the calcium carbonate and the at least two impurities from the first reacted slurry, producing a first filtrate, wherein the first filtrate is ammonium sulfate; an evaporator to evaporate water from the ammonium sulfate to produce an ammonium sulfate liquor; a crystallizer to crystallize and agglomerate the ammonium sulfate liquor, resulting in ammonium sulfate crystals; a centrifuge to separate the ammonium sulfate crystals from the ammonium sulfate liquor; a dryer to dry the ammonium sulfate crystals; a second reactor to combine and dissolve the calcium carbonate and the at least two impurities with a solvent, resulting in a second reacted slurry, the second reacted slurry comprising solutes of the at least two impurities, calcium, and at least one insoluble component; a second filter to separate the at least one insoluble component from the second liquor, resulting in a second filtrate comprising the solutes of the at least two impurities and a soluble calcium salt; a third reactor to combine the second filtrate with a first base to precipitate a first metal from the second filtrate, wherein the first base is added until the pH of the second filtrate increases to a first predetermined pH, and wherein the first metal is at least one of the at least two impurities;
67 a third filter to separate the first metal from the second filtrate, resulting in a third filtrate comprising the calcium and a solute of the second of the at least two impurities; a fourth reactor to combine the third filtrate with a second base to precipitate a second metal from the third filtrate, wherein the second base is added until the pH of the third filtrate increases to a second predetermined pH, wherein the second metal is the second of the at least two impurities; a fourth filter to separate the second metal from the third filtrate, resulting in a fourth filtrate comprising the calcium; a fifth reactor to combine the fourth filtrate with a soluble carbonate to precipitate a metal carbonate, from the fourth filtrate, wherein the metal carbonate is at least one of calcium carbonate, strontium carbonate and barium carbonate, and wherein the soluble carbonate is added until the pH of the fourth filtrate increases to a third predetermined pH; and a fifth filter to separate the metal carbonate from the fourth filtrate.
2. The system of claim 1 wherein the at least two impurities in the calcium sulfate feedstock includes at least two of iron, aluminum, magnesium, manganese, uranium, thorium, lanthanum, praseodymium, cerium, neodymium, yttrium, strontium, barium, and magnesium.
3. The system of claim 1 wherein the phosphogypsum feedstock further includes at least one of red mud from an aluminum process, slag from steel furnaces, ash, and mine tailings.
4. The system of claim 1 wherein the solvent is an acid.
5. The system of claim 1 wherein the first base includes at least one of sodium hydroxide, calcium hydroxide, potassium hydroxide, and ammonium hydroxide.
6. The system of claim 1 wherein the first predetermined pH is 4.
7. The system of claim 1 wherein the second base includes at least one of sodium hydroxide, calcium hydroxide, potassium hydroxide, and ammonium hydroxide.
8. The system of claim 1 wherein the first metal includes at least one of iron, aluminum, uranium, and thorium.
9. The system of claim 1 wherein the second predetermined pH is 9.
10. The system of claim 1 wherein the second metal includes at least one of manganese, lanthanum, praseodymium, cerium, neodymium, and yttrium.
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11. The system of claim 1 wherein the at least one insoluble component includes at least one of silicon, aluminum silicate, mullite, and carbon.
12. The system of claim 1 wherein the third predetermined pH is 13.
13. The system of claim 1 wherein the soluble carbonate includes at least one of sodium carbonate, carbon dioxide, ammonium carbonate, or potassium carbonate.
14. The system of claim 1 wherein each of the one or more first reactors is a continuously-stirred tank reactor or a plug-flow reactor.
15. The system of claim 1 wherein there is one first reactor.
16. The system of claim 1 wherein there are two first reactors.
17. The system of claim 1 wherein there are three first reactors.
18. The system of claim 1 wherein there are four first reactors.
19. The system of claim 1 wherein the second filtrate further comprises at least one of ammonium chloride and potassium chloride.
20. The system of claim 1 wherein the third filtrate further comprises at least one of aluminum hydroxide, magnesium hydroxide, uranium, and thorium.
21. The system of claim 1 wherein the fourth filtrate further comprises at least one of rare-earth elements, ammonium nitrate, sodium phosphate, potassium phosphate, ammonium phosphate, and sodium chloride.
22. The system of claim 1 wherein the calcium carbonate separated from the fourth filtrate is in the form of nanoparticles.
23. A system comprising: a phosphogypsum feedstock comprising calcium sulfate and at least three impurities; a mixer to combine ammonia gas, carbon dioxide, and water, resulting in an ammonium carbonate reagent solution; one or more first reactors to combine and react the phosphogypsum feedstock with the ammonium carbonate reagent solution, resulting in a first reacted slurry comprising calcium carbonate, ammonium sulfate, and the at least three impurities; a first filter to separate the calcium carbonate and the at least three impurities from the first reacted slurry, producing an ammonium sulfate filtrate;
an evaporator to evaporate water from the ammonium sulfate filtrate to produce an ammonium sulfate liquor; a crystallizer to crystallize and agglomerate the ammonium sulfate liquor, resulting in ammonium sulfate crystals; a centrifuge to separate the ammonium sulfate crystals from the ammonium sulfate liquor; a dryer to dry the ammonium sulfate crystals; a second reactor to combine and dissolve the calcium carbonate and the at least three impurities with a solvent, resulting in a second reacted slurry, the second reacted slurry comprising solutes of the at least three impurities, calcium, and at least one insoluble component; a second filter to separate the at least one insoluble component from the second liquor, resulting in a second filtrate comprising the solutes of the at least three impurities and a soluble calcium salt; a third reactor to combine the second filtrate with a first base to precipitate a first metal from the second filtrate, wherein the first base is added until the pH of the second filtrate increases to a first predetermined pH, and wherein the first metal is at least one of the at least three impurities; a third filter to separate the first metal from the second filtrate, resulting in a third filtrate comprising the calcium and a solute of the second and third of the at least three impurities; a fourth reactor to combine the third filtrate with a second base to precipitate a second metal from the third filtrate, wherein the second base is added until the pH of the third filtrate increases to a second predetermined pH, wherein the second metal is the second of the at least three impurities; a fourth filter to separate the second metal from the third filtrate, resulting in a fourth filtrate comprising the calcium and a solute of the third of the at least three impurities; a fifth reactor to combine the fourth filtrate with a third base to precipitate a third metal from the fourth filtrate, wherein the third base is added until the pH of the fourth
filtrate increases to a third predetermined pH, wherein the third metal is the third of the at least three impurities; a fifth filter to separate the third metal from the fourth filtrate, resulting in a fifth filtrate comprising the calcium; a sixth reactor to combine the fifth filtrate with a soluble carbonate to precipitate calcium carbonate from the fifth filtrate, wherein the soluble carbonate is added until the pH of the fifth filtrate increases to a fourth predetermined pH; a sixth filter to separate the calcium carbonate from the fifth filtrate.
24. The system of claim 24 wherein the third predetermined pH is 11.
25. The system of claim 24, wherein the at least three impurities includes at least three of iron, aluminum, magnesium, manganese, uranium, thorium, lanthanum, praseodymium, cerium, neodymium, yttrium, strontium, barium, and magnesium.
26. The system of claim 24, wherein the third metal includes magnesium.
27. A system comprising: a feedstock comprising calcium sulfate and at least two impurities; a mixer to combine ammonia gas, carbon dioxide, and water, resulting in an ammonium carbonate reagent solution; one or more first reactors to combine and react the feedstock with the ammonium carbonate reagent solution, resulting in a first reacted slurry, comprising calcium carbonate, ammonium sulfate, and the at least two impurities; a first filter to separate the calcium carbonate and the at least two impurities from the first reacted slurry, producing an ammonium sulfate filtrate; a second reactor to combine and dissolve the calcium carbonate and the at least two impurities with a solvent, resulting in a second reacted slurry, the second reacted slurry comprising solutes of the at least two impurities, calcium, and at least one insoluble component; a second filter to separate the at least one insoluble component from the second liquor, resulting in a second filtrate comprising the solutes of the at least two impurities and a soluble calcium salt; a third reactor to combine the second filtrate with a first base to precipitate a first metal from the second filtrate, wherein the first base is added until the pH of the second
filtrate increases to a first predetermined pH, and wherein the first metal is at least one of the at least two impurities; a third filter to separate the first metal from the second filtrate, resulting in a third filtrate comprising the calcium and a solute of the second of the at least two impurities; a fourth reactor to combine the third filtrate with a second base to precipitate a second metal from the third filtrate, wherein the second base is added until the pH of the third filtrate increases to a second predetermined pH, wherein the second metal is the second of the at least two impurities; a fourth filter to separate the second metal from the third filtrate, resulting in a fourth filtrate comprising the calcium; a fifth reactor to combine the fourth filtrate with a soluble carbonate to precipitate calcium carbonate from the fourth filtrate, wherein the soluble carbonate is added until the pH of the fourth filtrate increases to a third predetermined pH; and a fifth filter to separate the calcium carbonate from the fourth filtrate.
28. A system comprising: a feedstock comprising calcium sulfate and at least three impurities; a mixer to combine ammonia gas, carbon dioxide, and water, resulting in an ammonium carbonate reagent solution; one or more first reactors to combine and react the feedstock with the ammonium carbonate reagent solution, resulting in a first reacted slurry, comprising calcium carbonate, ammonium sulfate, and the at least three impurities; a first filter to separate the calcium carbonate and the at least three impurities from the first reacted slurry, producing an ammonium sulfate filtrate; a second reactor to combine and dissolve the calcium carbonate and the at least three impurities with a solvent, resulting in a second reacted slurry, the second reacted slurry comprising solutes of the at least three impurities, calcium, and at least one insoluble component; a second filter to separate the at least one insoluble component from the second liquor, resulting in a second filtrate comprising the solutes of the at least three impurities and a soluble calcium salt;
72 a third reactor to combine the second filtrate with a first base to precipitate a first metal from the second filtrate, wherein the first base is added until the pH of the second filtrate increases to a first predetermined pH, and wherein the first metal is at least one of the at least three impurities; a third filter to separate the first metal from the second filtrate, resulting in a third filtrate comprising the calcium and a solute of the second and third of the at least three impurities,; a fourth reactor to combine the third filtrate with a second base to precipitate a second metal from the third filtrate, wherein the second base is added until the pH of the third filtrate increases to a second predetermined pH, wherein the second metal is the second of the at least three impurities; a fourth filter to separate the second metal from the third filtrate, resulting in a fourth filtrate comprising the calcium and a solute of the third of the at least three impurities; a fifth reactor to combine the fourth filtrate with a third base to precipitate a third metal from the fourth filtrate, wherein the third base is added until the pH of the fourth filtrate increases to a third predetermined pH, wherein the third metal is the third of the at least three impurities; a fifth filter to separate the third metal from the fourth filtrate, resulting in a fifth filtrate comprising the calcium; a sixth reactor to combine the fifth filtrate with a soluble carbonate to precipitate calcium carbonate from the fifth filtrate, wherein the soluble carbonate is added until the pH of the fifth filtrate increases to a fourth predetermined pH; a sixth filter to separate the calcium carbonate from the fifth filtrate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP22805261.9A EP4337359A1 (en) | 2021-05-15 | 2022-05-16 | Systems and methods to recover value-added materials from gypsum |
| CA3218330A CA3218330A1 (en) | 2021-05-15 | 2022-05-16 | Systems and methods to recover value-added materials from gypsum |
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| Application Number | Priority Date | Filing Date | Title |
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| US17/321,437 | 2021-05-15 | ||
| US17/321,437 US11479472B2 (en) | 2019-01-24 | 2021-05-15 | Systems and methods to recover value-added materials from gypsum |
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| PCT/US2022/029451 WO2022245733A1 (en) | 2021-05-15 | 2022-05-16 | Systems and methods to recover value-added materials from gypsum |
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| EP (1) | EP4337359A1 (en) |
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| KR101588320B1 (en) * | 2012-08-10 | 2016-01-25 | 스파르스태인 테크놀로지스 엘엘씨 | Process for converting fgd gypsum to ammonium sulfate and calcium carbonate |
| US9682868B2 (en) * | 2015-01-30 | 2017-06-20 | Sparstane Technologies LLC | Partially continuous countercurrent process for converting gypsum to ammonium sulfate and calcium carbonate |
| PL412427A1 (en) * | 2015-05-20 | 2016-11-21 | Włodzimierz Merka | Method for complex utilization of phosphogypsum |
| CA3127106A1 (en) * | 2019-01-24 | 2020-07-30 | Elixsys Inc. | Systems and methods to treat flue gas desulfurization and metal-bearing waste streams to recover value-added materials |
| US11148956B2 (en) * | 2019-01-24 | 2021-10-19 | Elixsys, Inc. | Systems and methods to treat flue gas desulfurization waste to produce ammonium sulfate and calcium carbonate products |
| US11479472B2 (en) * | 2019-01-24 | 2022-10-25 | Elixsys, Inc. | Systems and methods to recover value-added materials from gypsum |
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