Methods and systems for utilizing carbide lime or slag

Patent metadata

Field	Value
Publication number	US-9902652-B2
Application number	US-201514694348-A
Country	US
Kind code	B2
Filing date	Apr 23, 2015
Priority date	Apr 23, 2014
Publication date	Feb 27, 2018
Grant date	Feb 27, 2018

Abstract

Provided herein are methods comprising a) treating a slag solid or carbide lime suspension with an ammonium salt in water to produce an aqueous solution comprising calcium salt, ammonium salt, and solids; b) contacting the aqueous solution with carbon dioxide from an industrial process under one or more precipitation conditions to produce a precipitation material comprising calcium carbonate and a supernatant aqueous solution wherein the precipitation material and the supernatant aqueous solution comprise residual ammonium salt; and c) removing and optionally recovering ammonia and/or ammonium salt using one or more steps of (i) recovering a gas exhaust stream comprising ammonia during the treating and/or the contacting step; (ii) recovering the residual ammonium salt from the supernatant aqueous solution; and (iii) removing and optionally recovering the residual ammonium salt from the precipitation material.

First claim

What is claimed is:

1. A method comprising:
a) treating a slag solid or carbide lime suspension with an ammonium salt in water to produce an aqueous solution comprising calcium salt, ammonium salt, and solids;
b) contacting the aqueous solution with carbon dioxide from an industrial process under one or more precipitation conditions to produce a precipitation material comprising calcium carbonate and a supernatant aqueous solution wherein the precipitation material and the supernatant aqueous solution comprise residual ammonium salt; and
c) removing and optionally recovering ammonia and/or ammonium salt using one or more steps of (i) recovering a gas exhaust stream comprising ammonia during the treating and/or the contacting step; (ii) recovering the residual ammonium salt from the supernatant aqueous solution; and (iii) removing and optionally recovering the residual ammonium salt from the precipitation material;
wherein the method further comprises separating the solids from the aqueous solution before the contacting step and adding the separated solids to the precipitation material as a filler.

2. The method of claim 1 , wherein the ammonium salt is ammonium chloride, ammonium sulfate, ammonium nitrate, or combinations thereof.

3. The method of claim 2 , wherein molar ratio of the ammonium salt:slag solid or ammonium salt:carbide lime suspension is between about 0.5:1 to 2:1.

4. The method of claim 1 , wherein the treating step further comprises adding anhydrous ammonia or an aqueous solution of ammonia.

5. The method of claim 1 , further comprising dewatering the precipitation material after step b) to separate the precipitate from the supernatant aqueous solution.

6. The method of claim 1 , wherein the residual ammonium salt is ammonium chloride, ammonium sulfate, ammonium sulfite, ammonium hydrosulfide, ammonium thiosulfate, or combinations thereof.

7. The method of claim 1 , further comprising recovering the residual ammonium salt from the supernatant aqueous solution using recovery process selected from the group consisting of thermal decomposition, pH adjustment, reverse osmosis, multi-stage flash, multi-effect distillation, vapor recompression, distillation, and combinations thereof.

8. The method of claim 7 , further comprising recycling the recovered residual ammonium salt back to the treating step of the process, the contacting step of the process, or combination thereof.

9. The method of claim 1 , wherein the step of recovering the gas exhaust stream comprising ammonia comprises subjecting the gas exhaust stream comprising ammonia to a scrubbing process wherein the scrubbing process comprises scrubbing the gas exhaust stream comprising ammonia with the carbon dioxide from the industrial process and water to produce a solution of ammonia.

10. The method of claim 9 , wherein the solution of ammonia comprises carbamate which is optionally recycled back to the contacting step.

11. The method of claim 1 , wherein the step (iii) of removing and optionally recovering the residual ammonium salt from the precipitation material comprises heating the precipitation material between about 300-360° C. to evaporate the ammonium salt from the precipitation material with optional recovery by condensation of the ammonium salt.

12. The method of claim 11 , wherein the calcium carbonate comprises reactive vaterite which stays in the precipitation material as reactive vaterite after heating in step (iii).

13. The method of claim 12 , wherein the heating of the precipitation material between about 300-360° C. is for more than about 10 minutes or between about 10-60 minutes.

14. The method of claim 11 , wherein the ammonium salt evaporates from the precipitation material in a form comprising ammonia gas, hydrogen sulfide gas, sulfur dioxide gas, hydrogen chloride gas, chlorine gas, or combinations thereof.

15. The method of claim 11 , wherein the aqueous solution, the supernatant solution, the precipitation material, or combinations thereof, further comprises sulfur compound and the step (iii) further comprises removing the sulfur compound in a form comprising hydrogen sulfide and/or sulfur dioxide gas from the precipitation material.

16. The method of claim 12 , further comprising after step (iii) adding water to the precipitation material comprising reactive vaterite and transforming the vaterite to aragonite wherein the aragonite sets and hardens to form cement or cementitious product.

17. The method of claim 16 , wherein the cementitious product is a formed building material selected from masonry unit, construction panel, conduit, basin, beam, column, slab, acoustic barrier, insulation material, and combinations thereof.

18. The method of claim 1 , wherein the solids comprise carbon, silica, or combination thereof.

19. The method of claim 1 , wherein the solids are between 1-40 wt % in the aqueous solution, in the precipitation material, or combination thereof.

20. The method of claim 1 , wherein the one or more precipitation conditions are selected from temperature, pH, pressure, ion ratio, precipitation rate, presence of additive, presence of ionic species, concentration of additive and ionic species, stirring, residence time, mixing rate, forms of agitation, presence of seed crystal, catalyst, membrane, or substrate, dewatering, drying, ball milling, and combinations thereof.

21. The method of claim 1 , wherein the one or more precipitation conditions that favor formation of the calcium carbonate comprise a pH of between 7-8.5 of the aqueous solution, temperature of the solution between 20-45° C., residence time of between 15-60 minutes, or combinations thereof.

Assignees

• Calera Corp

Inventors

• Devenney Martin
• Fernandez Miguel
• Chen Irvin
• Calas Guillaume
• Weiss Michael Joseph
• Tester Chantel Cabrera

Classifications

• C01C1/24

  Sulfates of ammonium (C01C1/14 takes precedence) · CPC title

• C01C1/164

  Ammonium chloride · CPC title

• C04B14/28

  of calcium · CPC title

• C04B28/02 Primary

  containing hydraulic cements other than calcium sulfates · CPC title

• Y02P40/18

  Carbon capture and storage [CCS] · CPC title