Processes for recovering metallic iron from source material
The process addresses the inefficiency in existing carbonyl iron powder production by using controlled carbonylation and decomposition with gaseous agents to achieve over 95% recovery of metallic iron from sponge iron, improving yield and purity.
Patent Information
- Authority / Receiving Office
- US · United States
- Patent Type
- Applications(United States)
- Current Assignee / Owner
- CVMR CORP
- Filing Date
- 2023-10-05
- Publication Date
- 2026-07-09
AI Technical Summary
Existing processes for producing carbonyl iron powder from sponge iron are inefficient, converting only about 70 to 80% of the iron, with existing technologies, and the yield is low, with only about 70 to 80% of the iron in the sponge feed being converted to iron carbonyl and subsequently decomposed to produce carbonyl iron powder, even under elevated conditions.
A process involving carbonylation and decomposition of a metallic iron-comprising material, including activation with gaseous hydrogen sulphide and carbon monoxide, under controlled subatmospheric and elevated temperature conditions, to enhance the production of iron carbonyl and mitigate the formation of iron sulphides.
This process significantly increases the recovery of metallic iron to over 95% by enhancing the conversion of sponge iron to iron carbonyl, achieving higher yields and purity in the carbonyl iron powder production.
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Figure US20260193727A1-D00000_ABST
Abstract
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefits of priority to United States Provisional Patent Application No. 63 / 425,148 , filed Nov. 14, 2022, titled PROCESSES FOR RECOVERING METALLIC IRON FROM SOURCE MATERIAL, the contents of which are hereby expressly incorporated into the present application by reference in their entirety.FIELD
[0002] The present disclosure relates to processes for recovering metallic elements from source materials via carbonylation.BACKGROUND
[0003] It is industry practice to produce carbonyl iron powder from sponge iron where the sponge iron is reacted with carbon monoxide at 2,500 psi operating pressure and at 170° C. temperature. Due to the physical and chemical nature of the sponge iron, even at this elevated operating conditions, and over a time duration of over 100 hours, only about 70 to 80% of the iron in the sponge feed is converted to iron carbonyl and subsequently thermally decomposed to produce carbonyl iron powder.SUMMARY
[0004] In one aspect, there is provided a process for recovering metallic iron from sponge iron, comprising: carbonylating a metallic iron-comprising derivative material, which is derived from the sponge iron, with effect that iron carbonyl is obtained, and effecting decomposition of the iron carbonyl.
[0005] In another aspect, there is provided a process for recovering metallic iron from a metallic iron-comprising material includes at least 60 weight % iron, based on the total weight of the metallic iron-comprising material, comprising: carbonylating a metallic iron-comprising derivative material, which is derived from the metallic iron-comprising material, with effect that iron carbonyl is obtained, and effecting decomposition of the iron carbonyl.
[0006] In another aspect, there is provided a process for recovering a metallic element from a metallic element-comprising material, comprising: contacting the metallic element-comprising material with a gaseous processing agent, with effect that an activated metallic element-comprising material is obtained, wherein the gaseous processing agent includes gaseous hydrogen sulphide and a carbonylating agent, carbonylating a metallic element-comprising derivative material, which is derived from the activated metallic element-comprising material, with effect that a carbonyl, of the metallic element, is obtained, and effecting decomposition of the carbonyl of the metallic element.
[0007] In another aspect, there is provided a process for recovering a metallic element from a metallic element-comprising material, comprising: emplacing the metallic element comprising material within a contacting zone, evacuating the contacting zone, after the evacuating, contacting the metallic element-comprising material with a gaseous processing agent within the contacting zone, with effect that an activated metallic element-comprising material is obtained, carbonylating a metallic element-comprising derivative material, which is derived from the activated metallic element-comprising material, with effect that a carbonyl, of the metallic element, is obtained, and effecting decomposition of the carbonyl of the metallic element.BRIEF DESCRIPTION OF DRAWINGS
[0008] The preferred embodiments of the process will now be described with reference to the following accompanying drawings, in which:
[0009] FIG. 1 is a flowsheet illustrating an embodiment of the process.DETAILED DESCRIPTION
[0010] There is provided a process for extracting elemental iron from a metallic iron-comprising material via carbonylation. An exemplary metallic iron-comprising material is sponge iron. Other exemplary metallic iron-comprising material, suitable for the described process, include iron ore reduced by hydrogen to metallic form, or iron bar used for structural construction. Further examples of metallic iron-comprising material include carbon steel and mild steel, as long as these materials have the required surface are for the gas / solid interaction.
[0011] In some embodiments, for example, the metallic iron-comprising material includes at least 60 weight % iron, based on the total weight of the metallic iron-comprising material. In some embodiments, for example, the metallic iron-comprising material includes from 60 weight % iron, based on the total weight of the metallic iron-comprising material, to 80 weight % iron, based on the total weight of the metallic iron-comprising material.
[0012] In some embodiments, for example, the sponge iron is produced by reducing iron ore, mostly by coal. Sponge iron is porous due to the reduction condition. Even though it is porous, since coal is used as the reducing source, the iron particles are partially coated with carbon, rendering sponge iron to be difficult to process through the carbonylation process.
[0013] In some embodiments, for example, the process includes subjecting the metallic iron-comprising material to size reduction (such as, for example, by grinding, crushing, and / or milling) such that the metallic iron-comprising material is a particulate material, wherein, in some embodiments, for example, at least 90 weight % of the particulate material has a particle size of less than 30 millimetres, such as, for example, less than 20 millimetres, such as, for example, less than ten (10) millimetres such as, for example, less than five (5) millimetres, such as, for example, less than three (3) millimetres.
[0014] In some embodiments, for example, the metallic iron-comprising material is contacted with a gaseous processing agent, which includes gaseous hydrogen sulphide, with effect that the surface of the metallic iron-comprising material is activated, and with effect that an activated metallic iron-comprising material is obtained. In some embodiments for example, the activation is with effect that the elemental iron become more reactive. The contacting of the metallic iron-comprising material and the gaseous processing agent is effectuated within a contacting zone
[0015] In some embodiments, for example, prior to the contacting, and while the metallic iron-comprising material is disposed within the contacting zone, the contacting zone is evacuated, with effect that the pressure within the contacting zone is subatmospheric. After the evacuation, the gaseous processing agent is supplied to the contacting zone such that the contacting of the metallic iron-comprising material and the gaseous processing agent is effectuated after the evacuation.
[0016] In some of these embodiments, for example, the evacuation is a first evacuation, and after the first evacuation, inert gaseous material (such as inert gaseous material including nitrogen, such as, for example, at least 95% volume nitrogen, based on the total volume of the inert gaseous material, such as, for example, at least 99 volume %, based on the total volume of the inert gaseous material) is supplied to the contacting zone, thereby breaking the vacuum and effecting dilution of gaseous material remaining within the contacting zone after the first evacuation. In this respect, the inert gaseous material becomes emplaced within the contacting zone. After the supplying of the inert gaseous material to the contacting zone, the contacting zone is evacuated, such that the contacting zone is subjected to a second evacuation, with effect that the pressure within the contacting zone is subatmospheric. After the second evacuation, the gaseous processing agent is supplied to the contacting zone such that the contacting of the metallic iron-comprising material and the gaseous processing agent is effectuated after the second evacuation.
[0017] In some embodiments, for example, while the contacting of the metallic iron-comprising material and the gaseous processing agent is being effectuated within the contacting zone, the contacting zone is disposed at a pressure of less than 50 psig. In some of these embodiments, for example, the contacting zone is disposed at a pressure of at least atmospheric pressure, and less than 50 psig. In those embodiments where contacting is effectuated in response to supplying of the gaseous processing agent to the contacting zone, in some of these embodiments, for example, the gaseous processing agent is supplied to the contacting zone at a pressure of at least atmospheric pressure and less than 50 psig. In some embodiments, for example, contacting of the metallic iron-comprising material and the gaseous processing agent at higher pressures is avoided so as to mitigate production of iron sulphides. In those embodiments where the contacting is effectuated in response to supplying of the gaseous processing agent to the contacting zone, in some of these embodiments, for example, the gaseous processing agent is supplied at a pressure of less than 35 psig. In some of these embodiments, for example, the gaseous processing agent is supplied at a pressure of less than 25 psig and at least atmospheric pressure.
[0018] In some embodiments, for example, while the contacting of the metallic iron-comprising material and the gaseous processing agent is being effectuated within the contacting zone, the contacting zone is disposed at a temperature of at least 170 degrees Celsius. In some of these embodiments, for example, the temperature of the contacting zone is from 170 degrees Celsius to 200 degrees Celsius. In some embodiments, for example, effecting the contacting at these temperatures assists with efficiently activating the metallic iron-comprising material.
[0019] In some embodiments, for example, the gaseous processing agent further includes a gaseous carbonylating agent, such as, for example, gaseous carbon monoxide. In some embodiments, for example, the volumetric ratio of the gaseous carbonylating agent to gaseous hydrogen sulphide, within the gaseous processing agent, is greater than at least 17:3, such as, for example, at least 23:2. In some embodiments, for example, the volumetric ratio of the gaseous carbonylating agent to gaseous hydrogen sulphide, within the gaseous processing agent, is defined within a range, and the range is from 17:3 to 19:1. In some of these embodiments, for example, the gaseous processing agent includes at least five (5) volume % gaseous hydrogen sulphide, based on the total volume of the gaseous processing agent. In some of these embodiments, for example, the gaseous processing agent includes at least eight (8) volume % gaseous hydrogen sulphide, based on the total volume of the gaseous processing agent. In some of these embodiments, for example, the gaseous processing agent includes a concentration of gaseous hydrogen sulphide that is defined within a range, and the range is from five (5) volume % gaseous hydrogen sulphide, based on the total volume of the gaseous processing agent, to 15 volume % gaseous hydrogen sulphide, based on the total volume of the gaseous processing agent. In some embodiments, for example, the inclusion of the gaseous carbonylating agent within the gaseous processing agent is for, amongst other things, encouraging the production of iron carbonyl, while discouraging the production of iron sulphides.
[0020] In some embodiments, for example, after the activated metallic iron-comprising material is obtained, a metallic iron-comprising pre-cursor carbonylation material, deriving from the activated metallic iron-comprising material, is contacted with a carbonylating agent, within a carbonylation zone, with effect that a carbonylation product is produced, and the carbonylation product includes iron carbonyl. In some embodiments, for example, the metallic iron-comprising precursor carbonylation material is the activated metallic iron-comprising material. In some embodiments, for example, the carbonylating agent includes carbon monoxide. In some embodiments, for example, the carbonylating agent is carbon monoxide. In some embodiments, for example, the carbonylation zone is disposed at a carbonylation zone pressure, and the carbonylation zone pressure is from 1,600 psig to 2,500 psig, and at a carbonylation zone temperature, and the carbonylation zone temperature is from 170 degrees Celsius to 200 degrees Celsius. In some embodiments, for example, the carbonylation zone pressure is relatively high due to the fact that iron has a relatively lower affinity to react with carbon monoxide (than, for example, nickel), and, in those embodiments where the iron source is sponge iron, in some of these embodiments, carbon is coating iron material and, therefore, interferes with reaction with carbon monoxide. In some embodiments, for example, the carbonylation zone and the contacting zone are the same zone.
[0021] In some embodiments, for example, the carbonylation product further includes one or more metal carbonyls, including nickel carbonyl. In some of these embodiments, for example, the carbonylation zone product is fractionated. In some of these embodiments, for example, the fractionation is effected via fractional distillation. In some of these embodiments, for example, the carbonylation product includes iron carbonyl and nickel carbonyl, and the fractionation is with effect that a nickel carbonyl-comprising material is recovered as an overhead gaseous product and an iron carbonyl-comprising material is recovered as a bottoms liquid product. In some embodiments, for example, each one of the products (recovered from the fractionation), independently, is subjected to thermal decomposition to effect recovery of a relatively pure form of the recovered metal (e.g. carbonyl iron powder and carbonyl nickel powder).
[0022] Further embodiments will now be described in further detail with reference to the following non-limitative examples.EXAMPLE NO. 1
[0023] 1.5 kg of sponge iron material was charged to the reactor and purged with nitrogen to remove oxygen. The reactor was then pressurized to 50 psig with gaseous hydrogen sulphide to activate the sponge iron material. Iron carbonylation was conducted at 2,500 psi carbon monoxide pressure and at 170 degrees Celsius. We observed a slower reaction kinetics than the nickel / H2S activation process. Only 55% of iron was extracted during this test in almost 70 hours.EXAMPLE NO. 2
[0024] The reactor was charged with 1.5 kg of sponge iron material. The reactor was then heated to a temperature of 170 degrees Celsius. At this temperature, the reactor was evacuated. After evacuation, the vacuum was broken and the reactor was pressurized to about 15 psig by introducing a gaseous mixture of 8 volume % gaseous hydrogen sulphide and 92 volume % gaseous carbon monoxide. The reactor was then pressurized to 1,800 psi with carbon monoxide. Within 48 hours, 95% of the iron was extracted as iron carbonyl.EXAMPLE NO. 3
[0025] The reactor was charged with 1.5 kg of sponge iron material. The reactor was then heated to a temperature of 170 degrees Celsius. At this temperature, the reactor was evacuated. After evacuation, the vacuum was broken and the reactor was pressurized to about 15 psig by introducing a gaseous mixture of 8 volume % gaseous hydrogen sulphide and 92 volume % gaseous carbon monoxide. The reactor was then pressurized to 1,500 psi with carbon monoxide. Within 70 hours, 90% of the iron was extracted as iron carbonyl.
[0026] In the above description, for purposes of explanation, numerous details are set forth in order to provide a thorough understanding of the present disclosure. However, it will be apparent to one skilled in the art that these specific details are not required in order to practice the present disclosure. Although certain dimensions and materials are described for implementing the disclosed example embodiments, other suitable dimensions and / or materials may be used within the scope of this disclosure. All such modifications and variations, including all suitable current and future changes in technology, are believed to be within the sphere and scope of the present disclosure. All references mentioned are hereby incorporated by reference in their entirety.
Claims
1. A process for recovering metallic iron from sponge iron, comprising: carbonylating a metallic iron-comprising derivative material, which is derived from the sponge iron, with effect that iron carbonyl is obtained; andeffecting decomposition of the iron carbonyl.
2. The process as claimed in claim 1;further comprising:prior to the carbonylating, contacting the sponge iron with gaseous hydrogen sulphide, with effect that an activated sponge iron is obtained;wherein:the metallic iron-comprising derivative material is derived from the activated sponge iron.
3. The process as claimed in claim 2;wherein:the contacting of the sponge iron with gaseous hydrogen sulphide is effectuated within a contacting zone; andthe contacting zone is disposed at a pressure of at least atmospheric pressure, and less than 50 psig.
4. The process as claimed in claim 2;the contacting of the sponge iron with gaseous hydrogen sulphide is effectuated in response to emplacement of gaseous processing agent within the contacting zone; andthe gaseous processing agent includes at least five (5) volume % gaseous hydrogen sulphide, based on the total volume of the gaseous processing agent.
5. The process as claimed in claim 4;wherein:the gaseous processing agent further includes a carbonylating agent; andthe volumetric ratio of the gaseous carbonylating agent to gaseous hydrogen sulphide, within the gaseous processing agent, is greater than at least 17:3.
6. The process as claimed as in claim 1;wherein:the carbonylating is effectuated within a carbonylation zone that is disposed at a carbonylation zone pressure, and the carbonylation zone pressure is from 1,600 psig to 2,500 psig.
7. The process as claimed in claim 6;wherein:while the carbonylating is being effectuated, the carbonylation zone is disposed at a carbonylation zone temperature, and the carbonylation zone temperature is from 170 degrees Celsius to 200 degrees Celsius.
8. A process for recovering metallic iron from a metallic iron-comprising material includes at least 60 weight % iron, based on the total weight of the metallic iron-comprising material, comprising:carbonylating a metallic iron-comprising derivative material, which is derived from the metallic iron-comprising material, with effect that iron carbonyl is obtained; andeffecting decomposition of the iron carbonyl.
9. The process as claimed in claim 8;further comprising:prior to the carbonylating, contacting the metallic iron-comprising material with gaseous hydrogen sulphide, with effect that an activated metallic iron-comprising material is obtained;wherein:the metallic iron-comprising derivative material is derived from the activated metallic iron-comprising material.
10. The process as claimed in claim 9;wherein:the contacting of the metallic iron-comprising material with gaseous hydrogen sulphide is effectuated within a contacting zone; andthe contacting zone is disposed at a pressure of at least atmospheric pressure, and less than 50 psig.
11. The process as claimed in claim 9;the contacting of the metallic iron-comprising material with gaseous hydrogen sulphide is effectuated in response to emplacement of gaseous processing agent within the contacting zone; andthe gaseous processing agent includes at least five (5) volume % gaseous hydrogen sulphide, based on the total volume of the gaseous processing agent.
12. The process as claimed in claim 11;wherein:the gaseous processing agent further includes a carbonylating agent; andthe volumetric ratio of the gaseous carbonylating agent to gaseous hydrogen sulphide, within the gaseous processing agent, is greater than at least 17:3.
13. The process as claimed as in claim 8;wherein:the carbonylating is effectuated within a carbonylation zone that is disposed at a carbonylation zone pressure, and the carbonylation zone pressure is from 1,600 psig to 2,500 psig.
14. The process as claimed in claim 13;wherein:while the carbonylating is being effectuated, the carbonylation zone is disposed at a carbonylation zone temperature, and the carbonylation zone temperature is from 170 degrees Celsius to 200 degrees Celsius.
15. A process for recovering a metallic element from a metallic element-comprising material, comprising:contacting the metallic element-comprising material with a gaseous processing agent, with effect that an activated metallic element-comprising material is obtained, wherein the gaseous processing agent includes gaseous hydrogen sulphide and a carbonylating agent;carbonylating a metallic element-comprising derivative material, which is derived from the activated metallic element-comprising material, with effect that a carbonyl, of the metallic element, is obtained; andeffecting decomposition of the carbonyl of the metallic element.
16. The process as claimed in claim 15;wherein:the volumetric ratio of the gaseous carbonylating agent to gaseous hydrogen sulphide, within the gaseous processing agent, is greater than at least 17:3.
17. The process as claimed in claim 15;wherein:the volumetric ratio of the gaseous carbonylating agent to gaseous hydrogen sulphide, within the gaseous processing agent, is from 17:3 to 19:1.
18. The process as claimed in claim 16;wherein:the gaseous processing agent includes at least five (5) volume % gaseous hydrogen sulphide, based on the total volume of the gaseous processing agent.
19. The process as claimed in claim 16;wherein:the concentration of the gaseous hydrogen sulphide within the gaseous processing agent is from five (5) volume % gaseous hydrogen sulphide, based on the total volume of the gaseous processing agent, to 15 volume % gaseous hydrogen sulphide, based on the total volume of the gaseous processing agent.
20. The process as claimed in claim 15;wherein:the carbonylating agent includes gaseous carbon monoxide.
21. The process as claimed in claim 15;wherein:the metallic element is iron, and the metallic element-comprising material includes at least 60 weight % iron, based on the total weight of the metallic iron-comprising material.
22. The process as claimed in claim 15;wherein:the metallic element is iron, and the metallic element-comprising material is sponge iron.
23. A process for recovering a metallic element from a metallic element-comprising material, comprising:emplacing the metallic element comprising material within a contacting zone;evacuating the contacting zone;after the evacuating, contacting the metallic element-comprising material with a gaseous processing agent within the contacting zone, with effect that an activated metallic element-comprising material is obtained;carbonylating a metallic element-comprising derivative material, which is derived from the activated metallic element-comprising material, with effect that a carbonyl, of the metallic element, is obtained; andeffecting decomposition of the carbonyl of the metallic element.
24. The process as claimed in claim 23;wherein:after the evacuating, and prior to the contacting of the metallic element-comprising material with a gaseous processing agent:supplying inert gaseous material into the contacting zone with effect that the inert gaseous material becomes emplaced within the contacting zone; andafter the inert gaseous material has become emplaced within the contacting zone, evacuating the contacting zone.
25. The process as claimed in claim 24;wherein:the evacuating prior to the supplying of the inert gaseous material is a first evacuating; andthe evacuating after the emplacing of the inert gaseous material within the contacting zone is a second evacuating;such that the contacting of the metallic element-comprising material with a gaseous processing agent is effectuated after the second evacuating.
26. The process as claimed in claim 23;wherein:the contacting of the metallic element-comprising material with a gaseous processing agent is effectuated by supplying the gaseous processing agent to the contacting zone.