EP3532445A1 - Efficient integration of manufacturing of upcycled concrete product into power plants - Google Patents
Efficient integration of manufacturing of upcycled concrete product into power plantsInfo
- Publication number
- EP3532445A1 EP3532445A1 EP17865241.8A EP17865241A EP3532445A1 EP 3532445 A1 EP3532445 A1 EP 3532445A1 EP 17865241 A EP17865241 A EP 17865241A EP 3532445 A1 EP3532445 A1 EP 3532445A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reactor
- carbonation
- fly ash
- flue gas
- leaching
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 46
- 239000004567 concrete Substances 0.000 title claims abstract description 40
- 230000010354 integration Effects 0.000 title description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 209
- 239000011575 calcium Substances 0.000 claims abstract description 88
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000003546 flue gas Substances 0.000 claims abstract description 61
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000007787 solid Substances 0.000 claims abstract description 28
- 239000002002 slurry Substances 0.000 claims abstract description 24
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 23
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 23
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 23
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007493 shaping process Methods 0.000 claims abstract description 7
- 239000010881 fly ash Substances 0.000 claims description 143
- 238000006243 chemical reaction Methods 0.000 claims description 67
- 238000002386 leaching Methods 0.000 claims description 37
- 239000007789 gas Substances 0.000 claims description 32
- 238000001556 precipitation Methods 0.000 claims description 27
- 239000000376 reactant Substances 0.000 claims description 25
- 150000002500 ions Chemical class 0.000 claims description 11
- 239000002893 slag Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000010146 3D printing Methods 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 230000007246 mechanism Effects 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 3
- 230000001939 inductive effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 50
- 238000000034 method Methods 0.000 description 40
- 238000009472 formulation Methods 0.000 description 30
- 239000000047 product Substances 0.000 description 29
- 230000008569 process Effects 0.000 description 28
- 239000000243 solution Substances 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 24
- 239000002245 particle Substances 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000005755 formation reaction Methods 0.000 description 20
- 230000002829 reductive effect Effects 0.000 description 16
- 229910021532 Calcite Inorganic materials 0.000 description 15
- 230000006870 function Effects 0.000 description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 11
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 241000894007 species Species 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000003245 coal Substances 0.000 description 9
- 238000011161 development Methods 0.000 description 9
- 230000018109 developmental process Effects 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 235000019738 Limestone Nutrition 0.000 description 7
- 239000004568 cement Substances 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 239000006028 limestone Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000005728 strengthening Methods 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- -1 magnesia Chemical class 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 230000036961 partial effect Effects 0.000 description 6
- 230000037361 pathway Effects 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- 239000012808 vapor phase Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 230000033558 biomineral tissue development Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 235000012241 calcium silicate Nutrition 0.000 description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000002918 waste heat Substances 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 239000010754 BS 2869 Class F Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000012717 electrostatic precipitator Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 235000014380 magnesium carbonate Nutrition 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002076 thermal analysis method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000004876 x-ray fluorescence Methods 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910000171 calcio olivine Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000003467 diminishing effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 229940075620 somatostatin analogue Drugs 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000001370 static light scattering Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000000153 supplemental effect Effects 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910001748 carbonate mineral Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LPTQBQUNGHOZHM-UHFFFAOYSA-N dicalcium;silicate;hydrate Chemical class O.[Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] LPTQBQUNGHOZHM-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009440 infrastructure construction Methods 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012933 kinetic analysis Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 238000004514 thermodynamic simulation Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/02—Portland cement
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/18—Carbon capture and storage [CCS]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- This disclosure generally relates to manufacturing processes of concrete products and systems for manufacturing concrete products.
- CCS Carbon capture and storage
- a manufacturing process of a concrete product includes: (1) extracting calcium from solids as portlandite; (2) forming a cementitious slurry including the portlandite; (3) shaping the cementitious slurry into a structural component; and (4) exposing the structural component to carbon dioxide sourced from a flue gas stream, thereby forming the concrete product.
- the solids include at least one of iron slag or steel slag.
- extracting the calcium includes subjecting the solids to leaching in a leaching reactor to yield an ion solution, and wherein the leaching reactor is operated using heat sourced from the flue gas stream.
- extracting the calcium further includes inducing precipitation of the ion solution in a precipitation reactor to yield the portlandite, and wherein the precipitation reactor is operated using heat sourced from the flue gas stream.
- forming the cementitious slurry includes combining fly ash with the portlandite.
- shaping the cementitious slurry includes casting, extruding, molding, pressing, or 3D printing of the cementitious slurry.
- exposing the structural component includes exposing, during an initial time period, the structural component to a first gas reactant having a first carbon dioxide concentration, followed by exposing, during a subsequent time period, the structural component to a second gas reactant having a second carbon dioxide concentration that is greater than the first carbon dioxide concentration.
- a system for manufacturing a concrete product includes: (1) a leaching reactor; (2) a precipitation reactor connected to the leaching reactor; and (3) a set of heat exchangers thermally connected to the leaching reactor and the precipitation reactor and configured to source heat from a flue gas stream.
- the set of heat exchangers includes a set of finned-tube heat exchangers.
- the system further includes a capacitive concentrator connected between the leaching reactor and the precipitation reactor.
- the capacitive concentrator includes a set of electrodes and an electrical source connected to the set of electrodes.
- the system further includes a carbonation reactor connected to the leaching reactor and the precipitation reactor and configured to source carbon dioxide from the flue gas stream.
- the system further includes a mixer connected between the leaching reactor, the precipitation reactor, and the carbonation reactor.
- the system further includes an extruder or a pressing, molding, or forming device connected between the mixer and the carbonation reactor.
- the carbonation reactor includes: (i) a reaction chamber; and (ii) a gas exchange mechanism connected to the reaction chamber and configured to: expose, during an initial time period, contents of the reaction chamber to a first gas reactant having a first carbon dioxide concentration; and expose, during a subsequent time period, the contents to a second gas reactant having a second carbon dioxide concentration that is greater than the first carbon dioxide concentration.
- a manufacturing process of a concrete product includes: (1) forming a cementitious slurry including fly ash; (2) shaping the cementitious slurry into a structural component; and (3) exposing the structural component to carbon dioxide sourced from a flue gas stream, thereby forming the concrete product.
- forming the cementitious slurry includes combining water with the fly ash.
- the fly ash includes calcium in the form of one or more calcium-bearing compounds (e.g., lime (CaO)) in an amount of at least about 15% by weight, at least about 18%> by weight, at least about 20% by weight, at least about 23% by weight, or at least about 25% by weight, and up to about 27% by weight, up to about 28% by weight, or more, along with silica (Si0 2 ) and oxides of metals.
- shaping the cementitious slurry includes casting, extruding, molding, pressing, or 3D printing of the cementitious slurry.
- the flue gas stream has a carbon dioxide concentration equal to or greater than about 3% (v/v).
- exposing the structural component includes exposing, during an initial time period, the structural component to a first gas reactant having a first carbon dioxide concentration, followed by exposing, during a subsequent time period, the structural component to a second gas reactant having a second carbon dioxide concentration that is greater than the first carbon dioxide concentration.
- Figure 1 An illustration of a manufacturing process flow and its integration into a primary exhaust stream of a coal-fired power plant.
- Figure 2 An illustration of capacitive concentration.
- Figure 3 An illustration of the integration of a process flow to tap a flue gas stream prior to and after desulfurization to secure waste heat, and to provide C0 2 for upcycled concrete production.
- FIG. 4 An illustration of a two-stage carbonation process. Conditions during an example setup for gas-fired flue gas stream are indicated.
- FIG. 1 A schematic of a carbonation reactor showing vapor streams, sample placement, and monitoring and control units (e.g., flow-meters, pressure regulators, temperature/relative humidity (T/RH) meters, and gas chromatograph (GC)).
- monitoring and control units e.g., flow-meters, pressure regulators, temperature/relative humidity (T/RH) meters, and gas chromatograph (GC)).
- Figure 6 The evolution of compressive strengths of: (a) Ca-rich and Ca-poor fly ash pastes following C0 2 exposure at about 75 °C, and the control samples (exposed to pure N 2 ) for comparison, as a function of (carbonation) time, (b) hydrated OPC pastes at different ages after curing in limewater at about 23 °C, as a function of w/s.
- the dashed black line shows the compressive strength of a Ca-rich fly ash formulation following its exposure to C0 2 at about 75 °C for about 7 days, (c) Ca-rich fly ash pastes carbonated at different temperatures following exposure to about 99.5% C0 2 (v/v) and simulated flue gas (about 12% CO 2 , v/v), as a function of time, and, (d) Ca-enriched (with added Ca(OH) 2 , or dissolved Ca(N0 3 ) 2 ) Ca-poor (Class F) fly ash pastes following C0 2 exposure at about 75 °C, as a function of time.
- the compressive strengths of the pristine Ca-poor fly ash with and without carbonation are also shown for comparison.
- 1/2FH 3 Fe(OH) 3
- 1/2AH 3 Al(OH) 3
- C-S-H calcium silicate hydrate.
- the solid phase balance is calculated until the pore solution is exhausted, or the fly ash reactant is completely consumed.
- Figure 8 Representative X-ray diffraction (XRD) patterns of Ca-rich and Ca-poor fly ash formulations before and after exposure to CO 2 at about 75 °C for about 10 days.
- the Ca-poor fly ash shows no noticeable change in the nature of compounds present following exposure to C0 2 .
- FIG. 9 Representative scanning electron microscopy (SEM) micrographs of: (a) a Ca-rich fly ash formulation following exposure to N 2 at about 75 °C for about 10 days; a magnified image highlighting the surface of a fly ash particle is shown in (b), (c) a Ca-rich fly ash formulation following exposure to pure C0 2 at about 75 °C for about 10 days; a magnified image highlighting the surface of a carbonated fly ash particle wherein carbonation products in the form of calcite are visible on the particle surface is shown in (d), (e) a Ca-poor fly ash formulation following exposure to pure CO 2 at about 75 °C for about 10 days, and (f) Ca(OH) 2 -enriched Ca-poor fly ash formulation following exposure to pure C0 2 at about 75 °C for about 10 days wherein the somewhat increased formation of calcite is noted on particle surfaces.
- SEM scanning electron microscopy
- FIG. 10 (a) The CO 2 uptake (normalized by the mass of Ca-rich fly ash in the formulation) as a function of time for samples exposed to pure CO 2 at different isothermal temperatures. The amount of C0 2 uptake was estimated using the mass-based method, (b) The compressive strength of the Ca-rich and Ca-poor fly ash samples as a function of their CO 2 uptake following exposure to pure CO 2 at different temperatures for up to about 10 days. The data reveals a strength gain rate of about 3.2 MPa per unit mass of fly ash that has reacted (carbonated). The amount of C0 2 uptake was estimated using the mass-based method, (c) The C0 2 uptake of a Ca-rich fly ash formulation as a function of depth.
- the macroscopic sample is composed of a cube (about 50 mm ⁇ about 50 mm ⁇ about 50 mm) that was exposed to pure C0 2 at about 75 °C for about 10 days.
- C0 2 uptake was assessed by thermal analysis (TGA).
- Figure 11 Fits of an equation for a generalized reaction-diffusion model to experimental carbonation data taken from Figure 7a for different carbonation temperatures.
- Embodiments of this disclosure are directed to an upcycled concrete product.
- the use of limestone as a cementation agent is leveraged to result in a C0 2 -negative concrete product.
- the upcycled concrete product leverages a process to secure calcium species for carbonate mineralization using industrial wastes as precursors or reactants, thereby eliminating the need for newly mined or produced materials.
- a carbonation process can efficiently utilize both C0 2 and waste heat carried by flue gas in a coal-fired power plant. In such manner, the upcycled concrete product and process can significantly enhance a C0 2 capturing capacity of a limestone-cement-based concrete product, and thereby can establish a C0 2 -negative process that can mitigate C0 2 emission at large scales.
- An upcycled concrete product is a transformative, C0 2 -negative construction material which provides a solution for C0 2 and industrial waste upcycling.
- a manufacturing process of the upcycled concrete product is designed to integrate as a bolt-on system to coal-fired power plants. Therefore, provision is made to secure flue gas, before desulfurization, as a heat transfer fluid, and post-desulfurization as a source of C0 2 (e.g., equal to or greater than about 3% C0 2 or about 12% C0 2 , v/v).
- heat provisioned by the flue gas is used to facilitate leaching and precipitation reactions (e.g., above about 20 °C, above about 25 °C, or above about 35 °C), and accelerate the carbonation kinetics (e.g., above about 20 °C, above about 25 °C, or above about 35 °C).
- the C0 2 present in the flue gas is systematically consumed by mineralization. By tapping the flue gas stream at two discrete points, extrinsic energy demands for upcycled concrete processing are reduced, without imposing additional demands for emissions control.
- a manufacturing process flow of some embodiments is illustrated in Figure 1. The initial stages involve leaching and precipitation of portlandite (Ca(OH) 2 ) particulates from reclaimed solids.
- the reclaimed solids can be in the form of either, or both, crystallized iron slags or steel slags rich in calcium (Ca) and magnesium (Mg).
- the slags can be formed as by-products of iron and steel manufacturing, and can include calcium in the form of simple oxides (e.g., lime (CaO)) in an amount of at least about 25% by weight, at least about 30% by weight, at least about 35% by weight, or at least about 40% by weight, and up to about 45% by weight, up to about 50% by weight, or more, along with silica (Si0 2 ) and oxides of metals, such as magnesia, alumina, manganese oxide, and iron oxide.
- simple oxides e.g., lime (CaO)
- silica (Si0 2 ) and oxides of metals such as magnesia, alumina, manganese oxide, and iron oxide.
- the slags can be suitably granulated in the form of granules to facilitate subsequent processing, such as through greater surface area and associated interface effects.
- the calcium present in the slags is leached or extracted by dissolution in, or exposure to, a leaching solution (e.g., an aqueous solution optionally including one or more leaching aids) to form a calcium ion solution in a leaching reactor 102 (e.g., a leaching tank) operated at a temperature in a range of about 20 °C to about 90 °C.
- a leaching solution e.g., an aqueous solution optionally including one or more leaching aids
- a resulting concentrated ion solution is induced to precipitate portlandite to yield a portlandite slurry in a precipitation reactor 106 (e.g., a precipitation tank) connected to the capacitive concentrator 104 and operated at a temperature in a range of about 70 °C to about 90 °C.
- a precipitation reactor 106 e.g., a precipitation tank
- capacitive concentration is performed by applying an electrical input from an electrical source 202 to a pair of electrodes 204 and 206 included in the capacitive concentrator 104, such that calcium ions in the leaching solution are drawn towards the electrodes 204 and 206, and subsequently can be released by reversing the electrical input to yield a higher concentration of the calcium ions.
- the portlandite slurry and leached slag granules are then combined with water, fly ash (or other coal combustion by-products), and fine and coarse aggregates using a mixer 108 to form a cementitious slurry (e.g., either a concrete or mortar concrete slurry), which is then shape-stabilized into structural components by an extruder 110 connected to the mixer 108.
- a cementitious slurry e.g., either a concrete or mortar concrete slurry
- suitable aggregates include sand, gravel, crushed stone, slag, recycled concrete, and so forth.
- Shape stabilization can yield the structural components as beams, columns, slabs, wall panels, cinder blocks, bricks, sidewalks, and so forth.
- a carbonation reactor 112 e.g., including a carbonation chamber operated at a temperature in a range of about 50 °C to about 70 °C to react with C0 2 sourced from a flue gas in a (water) condensing atmosphere at sub-boiling conditions.
- C0 2 sourced from a flue gas in a (water) condensing atmosphere at sub-boiling conditions.
- portlandite within a structural component is converted into limestone (or calcium carbonate (CaC0 3 )) by C0 2 mineralization.
- Such mineralized CaC0 3 can provide desirable mechanical properties and durability, as well as cementation by forming limestone around and between aggregates to bind the aggregates to one another. This stage forms a final concrete product as a mineralized, pre-fabricated upcycled concrete product.
- Fly ash also can serve as a calcium source, and upon slight dissolution or leaching fly ash surfaces can be activated at a relatively high pH (e.g., in portlandite-rich environments) to provide cohesion/cementation.
- the integration into a primary (exhaust) loop of a coal-fired power plant is achieved with two sub-systems: (I) a waste heat recycling subsystem, and (II) a two-stage carbonation sub-system.
- the flue gas of a coal-fired power plant typically features an outlet temperature between about 120 °C and about 180 °C.
- Thermal energy in the hot flue gas leaving a boiler is typically recovered by an economiser followed by an air pre-heater (APH).
- APH air pre-heater
- Flue gas heat recovery in the APH is performed until the flue gas temperature drops to about 150 °C (depending on the type of coal consumed) to mitigate against condensation of sulfuric acid (H 2 S0 4 ) on a surface of the APH and downstream ducts or other sub-systems.
- Cooling of the flue gas below an acid dew point can lead to acid condensation and deposition which in turn can cause corrosion, fouling, and plugging of the APH, the downstream ducts, and an electrostatic precipitator (ESP).
- ESP electrostatic precipitator
- fouling and plugging can result in increasing pressure drop and power consumption to force the flue gas through the APH.
- the flue gas leaving the ESP at about 150 °C to about 170 °C can be injected with activated carbon to remove mercury (Hg) traces before entering a flue gas desulfurization scrubber (FGD).
- FGD flue gas desulfurization scrubber
- the FGD can be a "wet" system composed of a spray tower in which the flue gas contacts a mist of droplets of an aqueous slurry of sorbent particles, such as hydrated lime or portlandite (Ca(OH) 2 ) and limestone (CaC0 3 ).
- sorbent particles such as hydrated lime or portlandite (Ca(OH) 2 ) and limestone (CaC0 3 ).
- Water evaporation reduces the flue gas temperature to about 50 °C to about 70 °C at which the desulfurization process is most efficient.
- the sorbent particles react with S0 2 in the flue gas to form insoluble calcium sulfite (CaS0 3 ), which reacts with oxygen to produce gypsum (CaS0 4 » 2H 2 0). In such manner, about 95% of the S0 2 is removed from the flue gas stream.
- the upcycled concrete manufacturing process taps or sources the flue gas line at about 150°C before the FGD to operate the leaching and precipitation reactors at about 20 °C to about 90 °C or about 70 °C to about 90 °C (depending on ambient weather and desired leaching rates) and re-injects colder flue gas back into the FGD, albeit above the dew point (e.g., > about 140 °C and up to, for example, about 160 °C).
- the integration points are illustrated in Figure 3.
- a set of finned-tube heat exchangers that transfer residual heat from the flue gas to a liquid water feeding the leaching and precipitation reactors 102 and 106 at an effectiveness of about 0.2 or greater can be used.
- a mass flow rate of the flue gas leaving the FTHX can be adjusted to ensure that the temperature does not fall below the acid dew point (e.g., about 140 °C).
- a temperature swing process can include a single pass crossflow heat exchanger (CFHX, see Figure 1) to transfer heat from the hot ion solution leaving the leaching reactor 102 to a solution feeding the leaching reactor 102.
- FTHX The choice of FTHX of some embodiments is given that a heat transfer coefficient on a flue gas side is small and therefore fins are desired to increase an effectiveness of liquid/gas heat exchange. However, for liquid/liquid heat exchange, a single pass CFHX is sufficient. Other types of heat exchangers also may be included.
- the upcycled concrete process can also divert the scrubbed flue gas that is secured post-desulfurization, namely after the FGD, into the carbonation reactor 112 (see Figure 3).
- the flue gas of a coal-fired power plant typically includes about 12% to about 15% of C0 2 (v/v).
- C0 2 is consumed and removed from the flue gas continuously.
- the C0 2 concentration reduces as carbonation proceeds, leading to diminishing C0 2 partial pressure towards a late stage of the reaction, which can adversely impact the reaction kinetics.
- the C0 2 partial pressure condition can be reversed by a two-stage carbonation process.
- a carbonation reaction is conducted using a gas with a low C0 2 concentration, such as an exhaust gas recycled at the end of the carbonation reaction.
- a gas with a low C0 2 concentration such as an exhaust gas recycled at the end of the carbonation reaction.
- the gas is replaced in a second stage by a C0 2 -rich flue gas, such as untreated flue gas or C0 2 -enriched flue gas, to finish a second stage of the carbonation reaction.
- the exhaust gas from the second stage is recycled and reused in the pre-carbonation stage to enhance a proportion of C0 2 captured.
- This process is flexible, and can incorporate C0 2 -enrichment technologies (e.g., membrane separation) and pressurization to further enhance the reaction kinetics and C0 2 capture efficiency.
- optimal process conditions for the two-stage carbonation can be determined from a process model.
- Figure 4 shows a sub-system of some embodiments for the carbonation process including a pressurized reaction chamber 400 integrated with a C0 2 -enrichment component 402 (e.g., configured to provide about 8.8x enrichment in C0 2 concentration) and pressurization up to about 2 MPa via a pair of mixer/compressors 404 and 406.
- the depicted sub-system can reduce an energy cost from compression by about 40% if a same level of C0 2 capture is obtained by compressing gas to compensate for the decrease in C0 2 partial pressure.
- the subsystem also uses about 50% less C0 2 -enriched gas to obtain an equal amount of C0 2 capture at a same throughput.
- a portion of a flue gas (e.g., having a C0 2 concentration of about 7.7 mol.%) is combined with a recycled gas (e.g., having a C0 2 concentration of about 37 mol.%) in the mixer/compressor 404 to obtain a pressurized gas mixture, which is then introduced into the pressurized reaction chamber 400 to perform a first stage carbonation of reagents in the form of a structural component.
- a flue gas e.g., having a C0 2 concentration of about 7.7 mol.
- a recycled gas e.g., having a C0 2 concentration of about 37 mol.
- Another portion of the flue gas is subjected to enrichment by the C0 2 -enrichment component 402 (e.g., to yield an enriched C0 2 concentration of about 68 mol.%), and is combined with the recycled gas in the mixer/compressor 406 to obtain a pressurized gas mixture, which is then introduced into the pressurized reaction chamber 400 to perform a second stage carbonation.
- a partial pressure of C0 2 (or a C0 2 concentration) in the gas mixture as introduced in the second stage of carbonation is greater than a partial pressure of C0 2 (or a C0 2 concentration) in the gas mixture as introduced in the first stage of carbonation.
- a controller 408 (e.g., including a processor 410 and an associated memory 412 connected to the processor 410 and storing processor-executable instructions) can be included to direct operation of various components of the sub-system shown in Figure 4.
- the two carbonation stages can be performed in the same pressurized reaction chamber 400 by replacing a gas phase reactant using a gas exchange mechanism (e.g., including a pump 414 and the mixer/compressors 404 and 406, along with valve(s), duct(s), and so forth) connected to the pressurized reaction chamber 400, without conveying partially carbonated solid or slurry materials from one chamber to another chamber.
- Additional carbonation stages can be included to implement multi-stage processes of two or more stages to further mitigate a drop in C0 2 partial pressure during each carbonation stage.
- OPC portland cement
- clinkering reactions involve substantial energy in the form of heat, and also result in the release of C0 2 from both the de-carbonation of limestone and the combustion of fuel to provide heat.
- this example demonstrates a route for clinkering-free cementation by carbonation of fly ash, which is a by-product of coal combustion. It is shown that in moist environments and at sub- boiling temperatures, Ca-rich fly ashes react readily with gas-phase C0 2 to produce robustly cemented solids.
- OPC-concrete has been used as the primary material for the construction of buildings and other infrastructure.
- the production of OPC is a highly energy - and C0 2 - intensive process.
- OPC production accounts for about 3% of primary energy use and results in about 9% of anthropogenic C0 2 emissions, globally.
- Such C0 2 release is attributed to factors including: (i) the combustion of fuel involved for clinkering the raw materials (limestone and clay) at about 1450 °C, and (ii) the release of C0 2 during the calcination of limestone in the cement kiln. As a result, about 0.9 tons of C0 2 are emitted per ton of OPC produced. Therefore, there is great demand to reduce the C0 2 footprint of cement, and secure alternative solutions for cementation for building and infrastructure construction.
- C0 2 is sequestered by the chemical reaction of C0 2 streams with light-metal oxides to form thermodynamically stable carbonates; thus allowing permanent and safe storage of C0 2 .
- different alkaline waste streams can be examined to render cementation solutions, the low production throughput, or severe operating conditions (high temperature and elevated C0 2 pressure) can render comparative solutions difficult to implement at a practical scale. Therefore, to synergize the utilization of two abundant by-products from coal-fired power plants (fly ash and C0 2 in flue gas), this example demonstrates clinkering-free cementation via fly ash carbonation. It is shown that Ca-rich fly ashes react readily with C0 2 under moist conditions, at atmospheric pressure and at sub-boiling temperatures. The influences of Ca availability in the fly ash, C0 2 concentration, and processing temperature on reaction kinetics and strength gain are discussed. Taken together, this example demonstrates routes for simultaneous valorization of solid wastes and C0 2 , in an integrated process.
- Class C (Ca-rich) and Class F (Ca-poor) fly ashes compliant with ASTM C618 were used.
- An ASTM CI 50 compliant Type I/II ordinary portland cement (OPC) was used as a cementation reference.
- the bulk oxide compositions of the fly ashes and OPC as determined by X-ray fluorescence (XRF) are shown in Table 1.
- the crystalline compositions of the Ca-rich and Ca-poor fly ashes as determined using X-ray diffraction (XRD) are shown in Table 2.
- fly ashes were used since they represent typical Ca-rich and Ca-poor variants in the United States, and since Ca content can strongly influence the extent of C0 2 uptake and strength development of carbonated fly ash formulations.
- Table 1 The oxide composition of fly ashes and OPC as determined using X-ray fluorescence (XRF).
- Table 2 The mineralogical composition of fly ashes and OPC as determined using quantitative X-ray diffraction (XRD) and Rietveld refinement.
- PSD particle size distribution
- SLS static light scattering
- IP A isopropanol
- the complex refractive index of OPC was taken as 1.70 + 0.10/.
- the uncertainty in the PSD was about 6% based on six replicate measurements. From the PSD, the specific surface area (SSA, units of m 2 /kg) of OPC was calculated by factoring in its density of about 3150 kg/m 3 , whereas the SSAs of the fly ashes were determined by N 2 -BET measurements.
- SSA specific surface area
- the compressive strengths of the fly ash cubes were measured at about 1 day intervals following ASTM CI 09 for up to about 10 days. All strength data reported in this example are the average of three replicate specimens cast from the same mixing batch.
- C0 2 uptake due to carbonation of the fly ashes was quantified by two methods: (i) a mass-gain method, and (ii) thermogravimetric analysis (TGA).
- the mass-gain method was used to estimate the average C0 2 uptake of the bulk cubic specimen from the mass gain of three replicate cubes following C0 2 contact as given by Equation (1): where, w (g/g) is the C0 2 uptake of a given cube, m t (g) is the mass of the specimen following C0 2 contact over a period of time t (days), m t (g) is the initial mass of the specimen, and m a (g) is the mass of dry fly ash contained in the specimen (estimated from the mixture proportions).
- w/ (g) is the final mass of a given cubical specimen following about 10 days of C0 2 exposure.
- TGA was used to determine the extent of C0 2 uptake at different depths in the fly ash cubes, from the surface to the center in about 5 mm increments. To accomplish so, cubes were sectioned longitudinally using a hand saw. Then, samples were taken from the newly exposed surface along a mid-line using a drill at a sampling resolution of about ⁇ 1 mm. The dust and debris obtained during drilling, at defined locations along the center-line, were collected and pulverized for thermal analysis in a PerkinElmer STA 6000 simultaneous thermal analyzer (TGA/DTG/DTA) provided with a Pyris data acquisition interface.
- TGA PerkinElmer STA 6000 simultaneous thermal analyzer
- thermodynamic calculations were carried out using GEM-Selektor, version 2.3 (GEMS).
- GEMS is a broad-purpose geochemical modeling code which uses Gibbs energy minimization criteria to compute equilibrium phase assemblages and ionic speciation in a complex chemical system from its total bulk elemental composition. Chemical interactions involving solid phases, solid solutions, and aqueous electrolyte(s) are considered simultaneously.
- the thermodynamic properties of all the solid and the aqueous species were sourced from the GEMS-PSI database, with additional data for the cement hydrates sourced from elsewhere.
- the Truesdell-Jones modification of the extended Debye-Hiickel equation see Eq.
- this solution phase model is suitable for / ⁇ 2.0 mol/kg beyond which, its accuracy is reduced.
- Ca-rich and Ca-poor fly ashes were reacted with water in the presence of a vapor phase composed of: (a) air (about 400 ppm C0 2 ), (b) about 12% C0 2 (about 88 % N 2 , v/v), and, (c) about 100% C0 2 (v/v).
- the solid phase balance was calculated as a function of degree of reaction of the fly ash, until either the pore solution is exhausted (constraints on water availability) or the fly ash is fully reacted.
- Figure 6(a) shows the compressive strength development as a function of time for Class C (Ca-rich) and Class F (Ca-poor) fly ash pastes carbonated in pure C0 2 at about 75 °C.
- the Ca-rich fly ash formulations show rapid strength gain following exposure to C0 2 , particularly during the first 6 days. For example, after about 3 days of C0 2 exposure, the carbonated formulation achieves a strength of about 25 MPa, whereas a strength on the order of about 35 MPa is produced after about 7 days of C0 2 exposure.
- FIG. 6(b) shows that the compressive strength of a Ca-rich fly ash formulation following exposure to C0 2 for about 7 days at about 75 °C - about 35 MPa - corresponds to that of an OPC formulation prepared at w/s of about 0.50 and cured in limewater at about 23 °C over the same time period. It is noted, however, that the fly ash formulations show a reduced rate of strength gain after about 7 days - likely due to the consumption of readily available species (Ca, Mg) that can form carbonate compounds.
- Ca, Mg readily available species
- OPC systems show a strength increase on the order of about 30%) from about 7 days to about 28 days (a common aging period that is noted in building codes) of maturation across all w/s.
- Figure 6(a) also indicates that, unlike the "carbonation strengthening" seen in Ca-rich fly ash formulations, Ca-poor fly ash systems showed a strength of ⁇ about 7 MPa even after about 10 days of carbonation, a gain of ⁇ about 2 MPa following C0 2 exposure vis-a-vis a system cured in a N 2 atmosphere.
- Ca-poor fly ashes feature reduced potential for C0 2 mineralization or strength gain following C0 2 exposure because the [Ca, Mg] available therein is either insufficient or not easily available for reaction (e.g., see Figure 8).
- carbonation strengthening is dominantly on account of the presence of reactive, alkaline compounds, namely Ca- and Mg-bearing compounds (e.g., CaO, MgO, and so forth), and Ca present in the fly ash glass (see Tables 1-2), that can react with C0 2 .
- Ca-rich fly ashes contain cementitious phases such as Ca 2 Si0 4 , Ca 2 Al 2 Si07, and Ca3Al 2 0 6 (see Table 2), which upon hydration (and carbonation) form cementitious compounds such as the calcium-silicate- hydrates (C-S-H), or in a C0 2 enriched atmosphere, calcite and hydrous silica (e.g., see Figures 7-8).
- C-S-H calcium-silicate- hydrates
- calcite and hydrous silica e.g., see Figures 7-8.
- the reactive crystalline compounds e.g., CaO, Ca 3 Al 2 06, and so forth
- the reactive crystalline compounds present in a Ca-rich fly ash are expected to rapidly dissolve in the first few minutes.
- alkaline species including Na, K, and Ca can be released progressively from the glassy compounds. This can result in the development of a silica-rich rim on the surfaces of fly ash particles. Pending the presence of sufficient solubilized Ca, and in the presence of dissolved C0 2 , calcite can form rapidly on the surfaces of leached (and other) particles, thereby helping proximate particles to adhere to each other as the mechanism of carbonation strengthening (e.g., see Figures 7-9).
- the enhancement in strength observed in the Ca-poor formulations is postulated to be on the account of both: (a) the pozzolanic reaction between the added Ca source and silica liberated from the fly ash resulting in the formation of calcium silicate hydrates (C-S- H), and, (b) the formation of calcite and (hydrous) silica gel by the carbonation- decomposition of C-S-H, and by direct reaction of solubilized Ca with aqueous carbonate species.
- the carbonation of C-S-H can result in the release of free water and the formation of a silica gel with reduced water content, as is also predicted by simulations (see Figure 7).
- Figure 9 the electron micrographs shown in Figure 9 provide additional insights into morphology and microstructure development in Ca-rich fly ash formulations following exposure to N 2 and C0 2 at about 75 °C for about 10 days.
- the un-carbonated fly ash formulations show a loosely packed microstructure with substantial porosity (Figure 9(a)). Close examination of a fly ash particle shows a "smooth" surface (e.g., see Figure 9(b)), although alkaline species might have been leached from the particle's surface.
- Figures 9(c-d) reveal the formation of a range of crystals that resemble "blocks and peanut-like aggregates" on the surfaces of Ca-rich fly ash particles - post- carbonation.
- Figure 10(a) shows C0 2 uptake by the Ca-rich fly ash formulation as determined by thermal analysis (by tracking the decomposition of CaC0 3 ) as a function of time across a range of curing temperatures. Both the rate and extent of C0 2 uptake, at a given time, increase with temperature. Although the terminal C0 2 uptake (which is a function of chemical composition) might be proposed to be similar across all conditions, this was not observed over the course of these experiments - likely due to kinetic constraints on dissolution, and the subsequent carbonation of the fly ash solids.
- mineral carbonation typically takes the form of irreversible heterogeneous solid-liquid-gas reactions.
- Ca-rich fly ashes it includes the processes of dissolution and hydration of the Ca-rich compounds including P-Ca 2 Si0 4 , Ca-rich glasses, CaO, Mg(OH) 2 , Ca(OH) 2 , and so forth, and the subsequent precipitation of CaC0 3 and MgC0 3 from aqueous solution, with reference to, for example, Table 2, Figure 7, and the following reactions:
- vapor phase C0 2 will dissolve in water, as dictated by its equilibrium solubility (as described by Henry's law) at the relevant pH and temperature.
- equilibrium solubility as described by Henry's law
- ionized species from the reactants and dissolved C0 2 accumulate in the liquid phase, up to achieving supersaturation - described by the ratio of the ion activity product to the solubility product for a given compound, such as calcite - precipitation occurs thereby reducing the supersaturation level.
- Ca- or Mg-bearing compounds in the fly ash would continue to dissolve as the solution remains under-saturated with respect to these phases due to the precipitation of carbonates, ensuring calcite and/or magnesite formation until the readily available quantity of these reactant compounds is exhausted and the system reaches equilibrium. It should be noted that in fly ash mixtures, wherein the abundance of alkaline compounds is substantial, where a large Ca/alkaline-buffer exists, the dissolution of gas-phase C0 2 which would otherwise acidify the pore solution has little impact on altering the solution pH.
- Equation (9) reduces to Jander's model for diffusion-controlled reactions, wherein the reaction rate is determined by the transport of reactants through the product layer to the reaction interface.
- Figure 11 shows fits of Equation (9) to the experimental carbonation data taken from Figure 10(a) for different carbonation temperatures.
- a clear change in slope is noted just prior to a reaction interval of about 2 days.
- Results set forth in this example demonstrate that exposure to concentrations of C0 2 in moist environments, at ambient pressure, and at sub-boiling temperatures can produce cemented solids whose properties are sufficient for use in structural construction. Indeed, Ca-rich fly ash solids, following C0 2 exposure achieve a strength of about 35 MPa after about 7 days or so, and take-up about 9% C0 2 by mass of reactants.
- Detailed results from thermodynamic modeling, XRD analyses, and SEM observations indicate that fly ash carbonation results in the formation of a range of reaction products, namely calcite, hydrous silica, and potentially some C-S-H which collectively bond proximate particles into a cemented solid.
- Such underutilization stems from the presence of impurities in the fly ash including unburnt carbon and calcium sulfate that forms due to the sulfation of lime that is injected for air pollution control (APC), compromising the durability of traditional concrete.
- the materials examined herein, namely fly ashes that are cemented by carbonation, should not be affected by the presence of such impurities - as a result, a wide range of Ca-rich fly ash sources - including those containing impurities, and mined from historical reservoirs ("ash ponds”) can be usable for carbonation-based fly ash cementation.
- fly ash carbonation can be effected at sub-boiling temperatures using dilute, untreated (flue-gas) C0 2 streams
- the outcomes of this example create a pathway for the simultaneous utilization of both solid- and vapor-borne wastes created during coal combustion.
- Such routes for waste, and especially C0 2 valorization create value-addition pathways that can be achieved without a need for carbon capture (or C0 2 concentration enhancement).
- the streamlined nature of this carbonation process ensures that it well-suited for co-location ("bolt-on, stack-tap" integration) with large point-source C0 2 emission sites including petrochemical facilities, coal/natural gas fired power plants, and cement plants.
- emitted flue gas can be used to provide both waste heat to hasten chemical reactions, and C0 2 to ensure mineralization without imposing additional criteria for emissions control.
- the proposed approach is significant since - within a lifecycle analysis (LCA) framework wherein there is no embodied C0 2 impact associated with reactants such as coal combustion wastes or emitted C0 2 , and wherein processing energy (heat) is secured from the flue gas stream - fly ash carbonation, by virtue of active C0 2 uptake, and C0 2 avoidance (by diminishing the production and use of OPC) has the potential to yield C0 2 negative pathways for cementation, and hence construction.
- LCA lifecycle analysis
- a set refers to a collection of one or more objects.
- a set of objects can include a single object or multiple objects.
- Objects of a set can be the same or different.
- connection refers to an operational coupling or linking.
- Connected objects can be directly coupled to one another or can be indirectly coupled to one another, such as via one or more other objects.
- the terms “substantially” and “about” are used to describe and account for small variations.
- the terms can refer to instances in which the event or circumstance occurs precisely as well as instances in which the event or circumstance occurs to a close approximation.
- the terms can refer to a range of variation of less than or equal to ⁇ 10% of that numerical value, such as less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, less than or equal to ⁇ 2%, less than or equal to ⁇ 1%), less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%).
- a first numerical value can be "substantially” or “about” the same as a second numerical value if the first numerical value is within a range of variation of less than or equal to ⁇ 10% of the second numerical value, such as less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, less than or equal to ⁇ 2%, less than or equal to ⁇ 1%), less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%.
- range format is used for convenience and brevity and should be understood flexibly to include numerical values explicitly specified as limits of a range, but also to include all individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly specified.
- a range of about 1 to about 200 should be understood to include the explicitly recited limits of about 1 and about 200, but also to include individual values such as about 2, about 3, and about 4, and sub-ranges such as about 10 to about 50, about 20 to about 100, and so forth.
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US11247940B2 (en) | 2016-10-26 | 2022-02-15 | The Regents Of The University Of California | Efficient integration of manufacturing of upcycled concrete product into power plants |
WO2019006352A1 (en) | 2017-06-30 | 2019-01-03 | The Regents Of The University Of California | Co2 mineralization in produced and industrial effluent water by ph-swing carbonation |
US11339094B2 (en) | 2017-08-14 | 2022-05-24 | The Regents Of The University Of California | Mitigation of alkali-silica reaction in concrete using readily-soluble chemical additives |
US11560318B2 (en) | 2017-08-18 | 2023-01-24 | The Regents Of The University Of California | Facile, low-energy routes for the production of hydrated calcium and magnesium salts from alkaline industrial wastes |
US11384029B2 (en) | 2019-03-18 | 2022-07-12 | The Regents Of The University Of California | Formulations and processing of cementitious components to meet target strength and CO2 uptake criteria |
US11254028B2 (en) | 2019-05-20 | 2022-02-22 | Saudi Arabian Oil Company | Systems and processes for accelerated carbonation curing of pre-cast cementitious structures |
EP3865202A1 (en) * | 2020-02-13 | 2021-08-18 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Use of co2-containing gaseous effluent in wet concrete preparation |
WO2021188682A1 (en) | 2020-03-20 | 2021-09-23 | The Regents Of The University Of Michigan | Sequestering carbon dioxide into precursors of bendabue engineered cementitious composites |
CN114033483B (en) * | 2021-11-24 | 2023-07-18 | 安徽马钢矿业资源集团姑山矿业有限公司 | Construction method suitable for collapse pit tailing filling process |
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US7413014B2 (en) * | 2003-12-19 | 2008-08-19 | Halliburton Energy Services, Inc. | Foamed fly ash cement compositions and methods of cementing |
WO2010006242A1 (en) * | 2008-07-10 | 2010-01-14 | Calera Corporation | Production of carbonate-containing compositions from material comprising metal silicates |
US7815880B2 (en) * | 2008-09-30 | 2010-10-19 | Calera Corporation | Reduced-carbon footprint concrete compositions |
EP2763783A4 (en) * | 2011-10-07 | 2015-07-15 | Richard J Hunwick | Process and system for capturing carbon dioxide from a gas stream |
WO2014005227A1 (en) * | 2012-07-03 | 2014-01-09 | Co2 Solutions Inc. | Slag stabilization with captured carbon dioxide |
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EP3129126A4 (en) * | 2014-04-07 | 2018-11-21 | Carboncure Technologies Inc. | Integrated carbon dioxide capture |
EP2952244B1 (en) * | 2014-06-02 | 2018-08-22 | General Electric Technology GmbH | Carbon capture system and method for capturing carbon dioxide |
WO2016061251A1 (en) * | 2014-10-15 | 2016-04-21 | The Regents Of The University Of California | Enhanced carbonation and carbon sequestration in cementitious binders |
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