Clinker and white portland cement with a high sulfur content derived from a high sulfur content pet-coke used as fuel

• US 20050126444A1
• Filed: 12/10/2003
• Published: 06/16/2005
• Est. Priority Date: 12/10/2002
• Status: Active Grant

• Current Assignee: Cemex Research Group AG (CEMEX España SA)
• Original Assignee: Cemex Trademarks Worldwide Ltd. (Cemex, S.A.B. De C.V.)
• Inventors: Castillo-Linton, Carlos Enrique, Eguia-Marquez, Graciela, Lopez-Gonzales, Waltter
• Granted Patent: US 7,001,454 B2
• Time in Patent Office: Days
• US Class Current: 106/739
• CPC Class Codes: C04B 2111/00215 Mortar or concrete mixtures defined by their oxide composition
• CPC Class Codes: C04B 2111/802 White cement
• CPC Class Codes: C04B 7/02 Portland cement
• CPC Class Codes: C04B 7/06 using alkaline raw materials C04B7/60 takes precedence
• CPC Class Codes: C04B 7/4407 Treatment or selection of the fuel therefor, e.g. use of hazardous waste as secondary fuel fuels in general C10L; Use of particular energy sources, e.g. waste hot gases from other processes

Abstract

The present invention relates to a family of white clinker compositions with a high capacity to fix sulfur derived from a high content pet-coke used as fuel in the manufacture thereof, which further exhibits low fuel consumption and fast setting, achieved by being comprised of the following amounts of clinker phases in percentage by weight: 3CaO.SiO₂ (C₃S): 40 to 75, 2CaO.SiO₂ (C₂S): 10 to 35, 3CaO.Al₂O₃ (C₃A): 0 to 15, CaO.SO₃ (CS): 0 to 10, 4CaO.3Al₂O₃.SO₃ (C₄A₃{haeck over (S)}): 2 to 15, 11CaO.7Al₂O₃.CaF₂ (C₁₁A₇.CaF₂): 0 to 5, total % CaF₂: 0.3 to 1.5 measured as CaF₂, % Fe₂O₃: 0 to 0.5 and a SO₃ content between 1.5 to 5% by weight obtained through the calcination of a raw meal containing CaO, SiO₂, Al₂O₃, and CaF₂, using as fuel, pet-coke with a sulfur content higher than 5% and at temperatures between 2192 and 2462° F., without the addiction of essentially any additive containing SO3 in the raw meal.

Claims

1. A white portland cement clinker, with the capacity to fix sulfur derived from an organic fuel having a high sulfur content, greater than 5% S, used as a fuel in the calcination of said clinker, said clinker additionally exhibiting reduced fuel consumption during such calcination and useful for producing a fast setting cement, and comprising amounts of clinker phases in percentage by weight, as follows:

3CaO.SiO₂ (C₃S);

40 to 75,

2CaO.SiO₂ (C₂S);

10 to 35,

3CaO.Al₂O₃ (C₃A);

0 to 15,

CaO.SO₃ (C{haeck over (S)});

0 to 10,

4CaO.3Al₂O₃.SO₃ (C₄A₃{haeck over (S)});

2 to 15,

11CaO.7Al₂O₃.CaF₂ (C₁₁A₇.CaF₂);

0 to 5,

Total % CaF₂;

0.3 to 1.5 measured as CaF₂,

% Fe₂O₃;

0 to 0.5,

and a SO₃ content between 1.5 and 5% by weight obtained through the calcination of a raw meal comprising CaO, SiO₂, Al₂O₃ and CaF₂, and using an organic fuel with a sulfur content higher than 5% as the main source of the clinker'"'"'s SO₃ content, at temperatures between 2192°

F. and 2462°

F., without the addition of any SO₃-containing additive to the raw meal as a main source of SO₃ content in the clinker.

2. The white portland cement clinker according to claim 1, wherein said clinker comprises the amounts of clinker phases in percentage by weight, as follows:

C₃S;

40 to 75,

C₂S;

10 to 35,

C{haeck over (S)};

0 to 10,

C₄A₃{haeck over (S)};

5 to 15,

C₁₁A₇.CaF₂;

2 to 5,

Total % CaF₂;

0.3 to 1.5 measured as CaF₂,

% Fe₂O₃;

<

0.5,

and a SO₃ content between 1.5 and 5% by weight obtained through the calcination of a raw meal mainly containing CaO, SiO₂, Al₂O₃ and CaF₂, using as fuel pet-coke with a sulfur content higher than 5%, at a temperature about 2282°

F., without any SO₃-containing additive to the raw meal as a main source of SO₃ content in the clinker, wherein the absence of C₃A results in a clinker useful in the manufacture of cements resistant to sulfates.

3. The white portland cement clinker according to claim 1, wherein said clinker comprises the amounts of clinker phases in percentage by weight, as follows:

C₃S;

40 to 75,

C₂S;

10 to 35,

C{haeck over (S)};

0 to 10,

C₄A₃{haeck over (S)};

5 to 15,

Total % CaF₂;

0.3 to 1.5 measured as CaF₂,

% Fe₂O₃;

<

0.5,

and a SO₃ content between 1.5 and 5% by weight obtained through the calcination of a raw meal mainly containing CaO, SiO₂, Al₂O₃ and CaF₂, using as fuel pet-coke with a sulfur content higher than 5% as the main source of the clinker'"'"'s SO₃ content, at a temperature about 2282°

F. without any SO₃-containing additive to the raw meal, wherein the absence of C₃A results in a clinker useful in the manufacture of cements resistant to sulfates.

4. The white portland cement clinker according to claim 1, wherein said clinker comprises the amounts of clinker phases in percentage by weight, as follows:

C₃S;

40 to 75,

C₂S;

10 to 35,

C₃A;

5 to 15,

C{haeck over (S)};

0 to 10,

C₄A₃{haeck over (S)};

2 to 10,

Total % CaF₂;

0.3 to 1.5 measured as CaF₂,

% Fe₂O₃;

<

0.5

and a SO₃ content between 1.5 and 5% by weight obtained through the calcination of a raw meal mainly containing CaO, SiO₂, Al₂O₃ and CaF₂, using as fuel pet-coke with a sulfur content higher than 5% as the main source of the clinker'"'"'s SO₃ content, at a temperature about 2462°

F., without any SO₃-containing additive to the raw meal

5. The white portland cement clinker according to claim 16, wherein the addition of the amounts of C₂S and C₃A clinker phases is higher than or equal to 10% by weight.

6. The white portland cement clinker according to claim 16, wherein the total CaF₂ percentage amount in the raw meal is from 0.2 to 1.0% by weight measured as CaF₂.

7. The white portland cement clinker according to claim 1, wherein the SO₃ content of the cement clinker is derived from pet-coke with a sulfur percentage higher than 5%.

8. The white portland cement clinker, according to claim 16, wherein the clinker SO₃ content is supplemented with other, inorganic, sources selected from the group consisting of plaster, anhydrite, and industrial debris containing sulfur.

9. The white portland cement clinker according to claim 16, wherein the alite, C₃S, and belite, C₂S, are crystals with sizes smaller than 25 micrometers, which provides a better ease of grinding than the conventional white Portland cement clinker.

10. The white portland cement clinker according to any of claims 2 to 4 and 16, wherein said clinker has a free lime percentage less than 1.5%.

11. A white portland cement comprising the cement clinker according to claim 16, wherein the SO₃ content of said cement is between 3.0 and 10%.

12. The white portland cement according to claim 11, wherein the specific area is 465 to 775 in²/g measured according to the ASTM C-204 standard through Blaine.

13. The white portland cement according to claim 11, wherein the initial setting time is between 10 and 45 minutes measured according to the ASTM C-191 standard through Vicat.

14. The white portland cement, according to claim 11, wherein the resistance to compression measured according to ASTM C-109 is about 15 to 25 N/mm² at 1 day, 25 to 35 N/mm² at 3 days, 40 to 55 N/mm² at 7 days, and 50 to 70 N/mm² at 28 days.

15. The white portland cement comprising the cement clinker according to claim 1, mixed with at least one of other materials selected from the group consisting of lime, slag, fly ash and other pozzolanic materials.

16. The white portland cement clinker according to claim 1, wherein the organic fuel is pet-coke.

17. The white portland cement according to claim 11, wherein the SO₃ content of the cement is 3.5-10 wt. %.

18. A method of producing a white Portland cement clinker according to claim 16, comprising:

subjecting a raw meal comprising CaO, SiO₂, Al₂O₃ and CaF₂, to a calcination at temperatures between 2192°

F., and 2462°

F.;

using pet-coke having a high sulfur content greater than 5% S as the calcination fuel and as the main source of the clinker'"'"'s SO₃ content;

said raw meal having been mixed so as to form upon calcination a white Portland cement clinker having phases in percentage by weight, as follows;

3CaO.SiO₂ (C₃S);

40 to 75,

2CaO.SiO₂ (C₂S);

10 to 35,

3CaO.Al₂O₃ (C₃A);

0 to 15,

CaO.SO₃ (C{haeck over (S)});

0 to 10,

4CaO.3Al₂O₃.SO₃ (C₄A₃{haeck over (S)});

2 to 15,

11CaO.7Al₂O₃.CaF₂ (C₁₁A₇.CaF₂);

0 to 5,

Total % CaF₂;

0.3 to 1.5 measured as CaF₂,

% Fe₂O₃;

0 to 0.5,

and a SO₃ content between 1.5 and 5% by weight, without the addition of any SO₃-containing additive to the raw meal as a main source of SO₃ content in the clinker.