US 11,773,017 B1Granted

Polluted CO2 capturing with lime produced from phosphogypsum calcination using sulfur as non-CO2 fuel

AssigneeSaudi Arabian Mining Company (Ma'aden)

InventorMalik Mohammad Odeh Aqel

Life of this patent

Estimating the term…

Abstract

A new integrated method to capture polluted CO2 using CaO produced from phosphogypsum calcination using sulfur as non-CO2 fuel where (1) both pollutants of phosphogypsum and CO2 are transformed into environmentally neutral or useful products such as limestone or clinker and sulfuric acid; (2) low-CO2 CaO produced from calcination of phosphogypsum with sulfur as fuel can be used to produce low-CO2 clinker that replaces the use of high-CO2 limestone as raw material; (3) the use of sulfur as fuel to calcine phosphogypsum allows the production of low-cost sulfuric acid.

Claims20

Dependent claims

An integrated method to capture polluted CO2 with CaO produced from phosphogypsum calcination using sulfur as non-CO2 fuel, comprising the steps of:

(a) flowing exhaust gases in counter current first to a phosphogypsum calcination plant and second to a drying plant where phosphogypsum is fed from dry stack, as described in reactions (i), (ii), (iii), and (iv):
(i) sulfur burning:
S+O2=SO2 at an approximate temperature range of approximately 1100 to 1400° C.;
(ii) CaSO4 calcination:
2CaSO4+C+heat=2CaO+2SO2+CO2;
where the reaction is carried out at an approximate temperature range of 1100 to 1400° C.;
(iii) pre-calcination of PG:
CaSO4.2H2O+heat=CaSO4+2H2O(v);
where the reaction is carried out at an approximate temperature range of approximately 650 to 950° C.;
(iv) drying of free moisture:
H2O(1)+heat=H2O(v);
where the reaction is carried out at an approximate temperature range of approximately 350 to 650° C.;
(b) treating a SO2-rich stream flowing from the phosphogypsum drying plant in a plant using limited Ca(OH)2 washing, as described in reactions (v) and (vi):
(v) 2Ca(OH)2+2SO2+O2=2CaSO4+H2O+heat;
(vi) Ca(OH)2+2CO=CaCO3+C+H2O+heat;
where cooling is applied to carry out reactions (v) and (vi) at an approximate temperature range of 350 to 400° C.;
and
feeding to a waste gas sulfuric acid plant;
(c) concentrating SO2-rich gas to a range of approximately 13 to 25% from the use of sulfur in the calcination plant with a reducing agent comprising C, and SO2 generated from PG calcination to a conventional sulfuric acid plant prior to the SO2 to SO3 conversion stage, where the SO2 is generated as described in reactions (vii) and (viii);
(vii) sulfur burning:
S+O2=SO2 carried out at a temperature range of approximately 1100-1400° C.;
(viii) CaSO4 calcination:
2CaSO4+C+heat=2CaO+2SO2+CO2;
where the reaction is carried out at a temperature range of approximately 1200 to 1400° C.;
(d) sulfuric acid production in conventional SAP is carried as well defined in the reactions (ix) and
(x):
(ix) 2SO2+O2=2SO3+heat;
where the reaction is carried out at an approximate temperature range of 350 to 500° C.;
(x) SO3+H2O=H2SO4+heat;
where the reaction is conducted at an approximate temperature range of approximately 75 to 165° C.;
(e) utilizing sulfuric acid produced in the waste gas sulfuric acid plant for digesting phosphate rock to obtain phosphoric acid and byproduct phosphogypsum;
(f) stacking phosphogypsum for the drying plant;
(g) reacting CaO powder produced in the calcination plant with CO2 in a circular fluid bed reactor to obtain CaCO3, as described in reactions (xi):
(xi) CaO+CO2=CaCO3+heat;
where reaction is carried out at a temperature below approximately 650° C.;
(h) where the CO2 from step (f) is produced by acidic fumes from a source selected from the group consisting of a phosphoric acid plant, hydrocarbon fuel combustion, and hydrogen reformers;
(i) Utilizing CaO powder to precipitate acid fumes from phosphogypsum calcination, as described in reactions (xii), (xiii), and (xiv):
(
xii
)
⁢
⁢
CaO
+
H
3
⁢
P
⁢
O
4
=
C
⁢
a
⁢
H
⁢
P
⁢
O
4
+
H
2
⁢
O
;
(
xiii
)
⁢
CaO
+
2
⁢
H
⁢
F
=
C
⁢
a
⁢
F
2
+
H
2
⁢
O
;
(
xiv
)
⁢
⁢
⁢
CaO
+
H
2
⁢
S
⁢
i
⁢
F
6
=
C
⁢
a
⁢
S
⁢
i
⁢
F
6
+
H
2
⁢
O
.

123 more elements

Dependencies are inferred from the claim text.

Facts

Application: 17/707,144Filed 29 Mar 2022
Priority: EP 2216473628 Mar 2022
Published: US 2023/0322619 A112 Oct 2023
Granted: 3 Oct 2023
Term ends: Not estimatedThe source records don’t support an estimate.

Classification19 codes

B01D 53/62
Removing components of defined structure: carbon oxides
C04B 7/367
Avoiding environmental pollution during cement-manufacturing: avoiding or minimising carbon dioxide emissions
B01D 53/501
Sulfur oxides: by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
C04B 7/365
Avoiding environmental pollution during cement-manufacturing: by extracting part of the material from the process flow and returning it into the…

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US 2023/0322619 A1Published application
US 11,773,017 B1This patent

From the US filing history. Foreign family members aren’t listed.

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Abstract

An integrated method to capture polluted CO2 with CaO produced from phosphogypsum calcination using sulfur as non-CO2 fuel, comprising the steps of:

(a) flowing exhaust gases in counter current first to a phosphogypsum calcination plant and second to a drying plant where phosphogypsum is fed from dry stack, as described in reactions (i), (ii), (iii), and (iv):
(i) sulfur burning:
S+O2=SO2 at an approximate temperature range of approximately 1100 to 1400° C.;
(ii) CaSO4 calcination:
2CaSO4+C+heat=2CaO+2SO2+CO2;
where the reaction is carried out at an approximate temperature range of 1100 to 1400° C.;
(iii) pre-calcination of PG:
CaSO4.2H2O+heat=CaSO4+2H2O(v);
where the reaction is carried out at an approximate temperature range of approximately 650 to 950° C.;
(iv) drying of free moisture:
H2O(1)+heat=H2O(v);
where the reaction is carried out at an approximate temperature range of approximately 350 to 650° C.;
(b) treating a SO2-rich stream flowing from the phosphogypsum drying plant in a plant using limited Ca(OH)2 washing, as described in reactions (v) and (vi):
(v) 2Ca(OH)2+2SO2+O2=2CaSO4+H2O+heat;
(vi) Ca(OH)2+2CO=CaCO3+C+H2O+heat;
where cooling is applied to carry out reactions (v) and (vi) at an approximate temperature range of 350 to 400° C.;
and
feeding to a waste gas sulfuric acid plant;
(c) concentrating SO2-rich gas to a range of approximately 13 to 25% from the use of sulfur in the calcination plant with a reducing agent comprising C, and SO2 generated from PG calcination to a conventional sulfuric acid plant prior to the SO2 to SO3 conversion stage, where the SO2 is generated as described in reactions (vii) and (viii);
(vii) sulfur burning:
S+O2=SO2 carried out at a temperature range of approximately 1100-1400° C.;
(viii) CaSO4 calcination:
2CaSO4+C+heat=2CaO+2SO2+CO2;
where the reaction is carried out at a temperature range of approximately 1200 to 1400° C.;
(d) sulfuric acid production in conventional SAP is carried as well defined in the reactions (ix) and
(x):
(ix) 2SO2+O2=2SO3+heat;
where the reaction is carried out at an approximate temperature range of 350 to 500° C.;
(x) SO3+H2O=H2SO4+heat;
where the reaction is conducted at an approximate temperature range of approximately 75 to 165° C.;
(e) utilizing sulfuric acid produced in the waste gas sulfuric acid plant for digesting phosphate rock to obtain phosphoric acid and byproduct phosphogypsum;
(f) stacking phosphogypsum for the drying plant;
(g) reacting CaO powder produced in the calcination plant with CO2 in a circular fluid bed reactor to obtain CaCO3, as described in reactions (xi):
(xi) CaO+CO2=CaCO3+heat;
where reaction is carried out at a temperature below approximately 650° C.;
(h) where the CO2 from step (f) is produced by acidic fumes from a source selected from the group consisting of a phosphoric acid plant, hydrocarbon fuel combustion, and hydrogen reformers;
(i) Utilizing CaO powder to precipitate acid fumes from phosphogypsum calcination, as described in reactions (xii), (xiii), and (xiv):
(
xii
)
⁢
⁢
CaO
+
H
3
⁢
P
⁢
O
4
=
C
⁢
a
⁢
H
⁢
P
⁢
O
4
+
H
2
⁢
O
;
(
xiii
)
⁢
CaO
+
2
⁢
H
⁢
F
=
C
⁢
a
⁢
F
2
+
H
2
⁢
O
;
(
xiv
)
⁢
⁢
⁢
CaO
+
H
2
⁢
S
⁢
i
⁢
F
6
=
C
⁢
a
⁢
S
⁢
i
⁢
F
6
+
H
2
⁢
O
.

123 more elements

Facts

Application

17/707,144Filed 29 Mar 2022

Priority

EP 2216473628 Mar 2022

Published

US 2023/0322619 A112 Oct 2023

Granted

3 Oct 2023

Term ends

Not estimatedThe source records don’t support an estimate.

Classification19 codes

B01D 53/62
Removing components of defined structure: carbon oxides
C04B 7/367
Avoiding environmental pollution during cement-manufacturing: avoiding or minimising carbon dioxide emissions
B01D 53/501
Sulfur oxides: by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
C04B 7/365
Avoiding environmental pollution during cement-manufacturing: by extracting part of the material from the process flow and returning it into the…