Microstructured carbonatable calcium silicate clinkers and methods thereof

• US 10,626,052 B2
• Filed: 02/12/2018
• Issued: 04/21/2020
• Est. Priority Date: 03/20/2015
• Status: Active Grant

• Current Assignee: Solidia Technologies, Inc.
• Original Assignee: Solidia Technologies, Inc.
• Inventors: Sahu, Sadananda, Quinn, Sean, Atakan, Vahit, DeCristofaro, Nicholas, Meyer, Vincent, Comparet, Cedric, Walenta, Gunther
• Primary Examiner(s): Ferre, Alexandre F
• Application Number:
  US15/894,826
• Publication Number:
  US 20180186696A1
• Time in Patent Office: 799 Days
• Field of Search: 428402
• CPC Class Codes: C04B 18/08 Flue dust , i.e. fly ash
• CPC Class Codes: C04B 18/141 Slags
• CPC Class Codes: C04B 18/146 Silica fume
• CPC Class Codes: C04B 2235/3206 Magnesium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3217 Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
• CPC Class Codes: C04B 2235/3272 Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
• CPC Class Codes: C04B 2235/3418 Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint glass constituents C04B2235/36
• CPC Class Codes: C04B 2235/349 Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
• CPC Class Codes: C04B 2235/5436 micrometer sized, i.e. from 1 to 100 micron
• CPC Class Codes: C04B 2235/80 Phases present in the sintered or melt-cast ceramic products other than the main phase
• CPC Class Codes: C04B 28/188 the Ca-silicates being present in the starting mixture
• CPC Class Codes: C04B 28/24 containing alkyl, ammonium or metal silicates; containing silica sols reaction mixtures resulting in mineral polymers C04B28/006; polymeric reaction products of alkali metal silicates with isocyanates C08G18/3895
• CPC Class Codes: C04B 35/22 rich in calcium oxide , e.g. wollastonite C04B35/195 takes precedence
• CPC Class Codes: C04B 35/64 Burning or sintering processes C04B33/32 takes precedence ; powder metallurgy B22F
• CPC Class Codes: C04B 40/0231 Carbon dioxide hardening
• CPC Class Codes: C04B 7/345 Hydraulic cements not provided for in one of the groups C04B7/02 - C04B7/34
• CPC Class Codes: Y02P 40/10 Production of cement, e.g. improving or optimising the production methods; Cement grinding
• CPC Class Codes: Y02P 40/18 Carbon capture and storage [CCS]
• CPC Class Codes: Y02W 30/91 Use of waste materials as fillers for mortars or concrete

Abstract

The invention provides novel, microstructured clinker and cement materials that are characterized by superior grindability and reactivity. The disclosed clinker and cement materials are based on carbonatable calcium silicate and can be made from widely available, low cost raw materials via a process suitable for large-scale production. The method of the invention is flexible in equipment and processing requirements and is readily adaptable to manufacturing facilities of conventional Portland cement.

Claims

1. A non-hydraulic clinker material, comprising:

particles of uncarbonatable silica (SiO₂), having diameters from about 0.1 μ

m to about 1,000 μ

m, dispersed in a matrix of the clinker, the matrix comprising at least one carbonatable calcium silicate phase,

wherein the at least one carbonatable calcium silicate phase comprises at least one of wollastonite and pseudowollastonite and at least one of rankinite (Ca₃ Si₂O₇) and belite (Ca₂SiO₄).

2. The clinker material of claim 1, further comprising an intermediate layer, comprising melilite ((Ca,Na,K)₂ (Al,Mg,Fe)[(Al,Si)SiO₇]) and/or an amorphous phase and surrounding the particles of uncarbonatable silica.

3. The clinker material of claim 2, wherein the intermediate layer comprises an amorphous phase comprising one or more components selected from Al₂O₃, Fe₂O₃, MgO, K₂O and Na₂O.

4. The clinker material of claim 1, wherein the clinker is suitable for carbonation with CO₂ at a temperature of about 30°

C. to about 90°

C. to form CaCO₃, under an atmosphere of water and CO₂having a pressure in the range from ambient atmospheric pressure to about 150 psi above ambient and having a CO₂ concentration ranging from about 10% to about 99% for about 1 hour to about 150 hours, with a mass gain of about 10% or more.

5. The clinker material of claim 4, wherein the clinker is suitable for carbonation with CO₂ at a temperature of about 40°

C. to about 80°

C. to form CaCO₃, under an atmosphere of water and CO₂ having a pressure in the range from ambient atmospheric pressure to about 40 psi above ambient and having a CO₂ concentration ranging from about 50% to about 95% for about 10 hour to about 50 hours, with a mass gain of about 10% or more.

6. The clinker material of claim 5, comprising about 30% or less of metal oxides of Al, Fe and Mg by total oxide mass.

7. A composite material produced by carbonation of a clinker material of claim 1.

8. A powdery material produced by grinding the clinker material of claim 1, wherein the powdery material is characterized by

a mean particle size (d50) of about 8 μ

m to about 25 μ

m, with 10% of particles (d10) sized below about 0.1 μ

m to about 3 μ

m, and 90% of particles (d90) sized between about 30 μ

m to about 100 μ

m; and

a surface at least 10% covered with the at least one carbonatable phase.

9. The powdery material of claim 8, wherein the particles comprise single-phase particles and multi-phase particles.

10. The powdery material of claim 9, wherein the single- phase particles comprise:

single-phase particles of carbonatable phases selected from wollastonite (CaSiO₃), rankinite (Ca₃Si₂O₇) and C2S (Ca₂SiO₄);

single-phase particles of partially reactive amorphous phases;

or single-phase particles of uncarbonatable phases selected from melilite ((Ca,Na,K)₂[(Mg, Fe²⁺,Fe^3+,Al,Si)₃O₇]) and crystalline silica (SiO₂);

or a combination of any two or more types thereof.

11. The powdery material of claim 9, wherein the multi-phase particles comprise:

multi-phase particles having a combination of two or more reactive phases;

multi-phase particles having a combination of at least one reactive phase with at least one uncarbonatable phase;

multi-phase particles having a combination of two or more uncarbonatable phases;

multi-phase particles having a combination of at least one reactive phase with a partially reactive amorphous phase;

multi-phase particles having a combination of at least one uncarbonatable phase with a partially reactive amorphous phase;

multi-phase particles having a combination of at least one reactive phase with at least one uncarbonatable phase and a partially reactive amorphous phase;

or multi-phase particles that have internal or surface connected voids;

or a combination of any two or more types thereof.

12. A method for making a clinker material, comprising:

mixing one or more precursors to obtain a blended precursor composition wherein metal oxides of Al, Fe and Mg are present at about 30% or less by mass; and

heating the blended precursor composition to a temperature between about 800°

C. and about 1400°

C. for a sufficient time to produce the clinker material,

wherein, the clinker material is non-hydraulic and comprises particles of uncarbonatable silica (SiO₂) having diameters from about _0.1 μ

m to about 1,000 μ

m, dispersed in a matrix of the clinker, the matrix comprising at least one carbonatable calcium silicate phase, and wherein the at least one carbonatable calcium silicate phase comprises at least one of wollastonite and pseudowollastonite and at least one of rankinite (Ca₃ Si₂O₇) and belite (Ca₂SiO₄).

13. A clinker material produced according to the method of claim 12.

14. The method of claim 12, wherein metal oxides of Al, Fe and Mg are present at about 10% or less by mass.

15. The method of claim 12, wherein the precursors are selected from limestone, sand, silts, sandstones, silica-rich clays and diatomaceous earths.

16. The method of claim 13, wherein the blended precursor composition is heated to a temperature between about 1,000°

C. and about 1,400°

C. for a sufficient time to produce the clinker material.

17. The method of claim 13, wherein the blended precursor composition is heated for a period of about 10 minutes to 5 hours.

18. The method of claim 13, wherein heating the blended precursor composition is conducted under atmospheric pressure.