The present subject matter relates to the production of inert slag, aluminum fluoride (AlF3) and energy and, more particularly, by converting Spent Pot Lining (SPL).
In core aluminum manufacturing processes, a high-temperature electrolysis cell converts alumina to aluminum metal. The cell, colloquially called pot, is lined with carbon (the cathode) and with multiple layers of refractory bricks (
An aluminum smelter produces up to 25,000 tons of SPLs per year3. All the 270 or so aluminum smelters around the world must handle such waste stream, which amounts to more than 1,500,000 metric tons per year worldwide. The SPL is a hazardous residual material because of its high content of leachable fluorides and cyanides. Moreover, SPL reacts with water to generate explosive gases, such as methane and hydrogen. Hence, transportation, remediation and final storage of SPL is subject to strict regulations. SPL is highly heterogeneous5, which complicates any recycling treatment. Still today, due to these considerations, the most common route to treat SPL is to dump it directly into highly secured (and expensive) landfills.
Commercial Alternatives to SPL Landfill
Many companies have worked to develop processes to decontaminate SPL, to recover or valorize the SPL carbon value and to recover the SPL fluoride value. The process alternatives to landfilling divide into either leaching or thermal destruction. Both alternatives have advantages and disadvantages. The most advanced decontamination processes for each process alternative are described hereinbelow.
Leaching: SPL decontamination and carbon recycling via low-caustic leaching and liming (LCL&L)
A major current alternative to SPL landfilling (or forever storage) is the low-caustic leaching and liming (LCL&L) process6. Rio Tinto currently operates an 80,000-ton/year LCL&L plant in the Saguenay region, Quebec. The process has the uttermost advantage of having already been through a difficult and long scale-up. Nonetheless, the process suffers from its complexity.
The following describes some of the process' complexity:
Thus, the major drawback of the LCL&L process is that it does not reduce the amount of solid wastes (1.17 kg solid by-product per 1 kg SPL), not counting all the liquid wastes. The process literally creates a new type of solid waste with a different decontamination challenge.
Thermal destruction: SPL decontamination and carbon valorization via a burner-powered thermal treatment
The other major current alternative process to SPL landfilling is the thermal degradation of SPL and the mechanical sorting of the degraded solid residue. The alternative process degrades the cyanides, volatilises the acid components and produces an inert sand from a SPL feedstock. The sand is sorted into carbon and refractories in a subsequent processing step to manufacture valuable by-products for the cement industry.
This process alternative is the basis of a commercial process that produces specialty carbon bricks and specialty inorganic salts from SPL9. The process is being used in Australia since the early 2000s and its major advantage is that it is mostly dry.
This process is well established but suffers drawbacks as well:
Here again, the major drawback of this batch-mode process is that it does not lower the amount of solid wastes.
Therefore, it would be desirable to provide an apparatus and a process that provide a reliable solution to the above problem afflicting core aluminum manufacturing processes.
It would thus be desirable to provide a novel apparatus and process for converting Spent Pot Lining (SPL) into inert slag, aluminum fluoride (AlF3) and energy.
The embodiments described herein provide in one aspect a process for converting spent pot linings (SPL), comprising a plasma arc furnace, a dry syngas cleaning train and an aluminum fluoride (AlF3) reactor,
a. the plasma arc furnace including an anode and a cathode, wherein:
i. the plasma arc furnace is adapted to gasify carbon to syngas;
ii. the plasma arc furnace is adapted to convert a mineral fraction to vitrified slag;
iii. steam is used to capture an excess energy from a gasification reaction and contributes to raise a syngas hydrogen content;
b. a cyclone at an outlet of the plasma arc furnace being adapted to collect dust particles;
c. the reactor being adapted to convert hydrogen fluoride (HF) in the syngas to AlF3;
d. a waste heat boiler being adapted to cool down the syngas and to be possibly used for energy recovery;
e. a baghouse is adapted to recover at least part of the dust particles not recovered by the cyclone, wherein the dry syngas typically has a very low dew point, avoiding condensation
Also, the embodiments described herein provide in another aspect a process, wherein a temperature of the plasma arc furnace is between 500° C. and 1800° C.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a vitrification of inert constituents of the SPL is carried out without requiring adding a slag agent, such as calcium oxide.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a conversion of HF to AlF3 is adapted to take place at a temperature higher than 500° C. but below 1000° C.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a source of Al2F3 to produce AlF3 is feed material to an aluminum electrolyser, purified Al2F3, or an intermediary aluminum hydroxide in a Bayer process.
Furthermore, the embodiments described herein provide in another aspect a process, wherein the reaction heat produced by a neutralisation of HF by Al2F3 is adapted to produce more steam in a heat recovery boiler (for instance HX-0411).
Furthermore, the embodiments described herein provide in another aspect a process, wherein any excess heat from the gasification of SPL in the plasma arc furnace is adapted to be used for converting water vapor (steam) or liquid water to hydrogen.
Furthermore, the embodiments described herein provide in another aspect a process, wherein the water is bled from the condensate-steam loop that flows in the waste heat recovery boiler (HX-0411).
Furthermore, the embodiments described herein provide in another aspect a process, wherein an oxidizing medium includes a mixture of air and water.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a hydrogenation of fluorine volatized from the SPL is achieved via steam reaction.
Furthermore, the embodiments described herein provide in another aspect a process, wherein the slag can be valorized as a concrete additive.
Furthermore, the embodiments described herein provide in another aspect a process, wherein the plasma SPL gasification and vitrification furnace is adapted to maintain a certain amount of feed material on top of a molten inorganic bath, ensuring a substantially complete temperature gradient in the plasma arc furnace, thereby allowing for drying, pyrolysis and partial combustion of the SPL.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a plasma SPL processing system requires only electricity as its energy source, i.e. no fossil fuels.
Furthermore, the embodiments described herein provide in another aspect a process for converting spent pot linings (SPL) into inert slag, aluminum fluoride (AlF3) and energy in the form of steam and syngas.
Furthermore, the embodiments described herein provide in another aspect a process, wherein the inert slag can be valorized as a concrete additive.
Furthermore, the embodiments described herein provide in another aspect a process for converting spent pot linings (SPL), comprising a plasma arc furnace, a dry syngas cleaning train and an aluminum fluoride (AlF3) reactor,
a. the plasma arc furnace including an anode and a cathode, wherein:
i. the plasma arc furnace is adapted to gasify carbon to syngas;
ii. the plasma arc furnace is adapted to convert a mineral fraction to vitrified slag;
iii. steam is used to capture an excess energy from a gasification reaction and contributes to raise a syngas hydrogen content;
b. a cyclone at an outlet of the plasma arc furnace being adapted to collect dust particles;
c. the reactor being adapted to convert hydrogen fluoride (HF) in the syngas to AlF3;
d. a waste heat boiler being adapted to cool down the syngas; and
e. a baghouse is adapted to recover at least part of the dust particles not recovered by the cyclone.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a temperature of the plasma arc furnace is between 500° C. and 1800° C.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a vitrification of inert constituents of the SPL is carried out without requiring adding a slag agent, such as calcium oxide.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a conversion of HF to AlF3 is adapted to take place at a temperature higher than 500° C. but below 1000° C.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a source of Al2F3 to produce AlF3 is feed material to an aluminum electrolyser, purified Al2F3, or an intermediary aluminum hydroxide in a Bayer process.
Furthermore, the embodiments described herein provide in another aspect a process, wherein reaction heat produced by a neutralisation of HF by Al2F3 is adapted to produce more steam in a heat recovery boiler (for instance HX-0411).
Furthermore, the embodiments described herein provide in another aspect a process, wherein any excess heat from the gasification of SPL in the plasma arc furnace is adapted to be used for converting water vapor (steam) or liquid water to hydrogen.
Furthermore, the embodiments described herein provide in another aspect a process, wherein water is bled from a condensate-steam loop that flows in a waste heat recovery boiler (HX-0411).
Furthermore, the embodiments described herein provide in another aspect a process, wherein an oxidizing medium includes a mixture of air and water.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a hydrogenation of fluorine volatized from the SPL is achieved via steam reaction.
Furthermore, the embodiments described herein provide in another aspect a process, wherein the slag can be valorized as a concrete additive.
Furthermore, the embodiments described herein provide in another aspect a process, wherein the plasma SPL gasification and vitrification furnace is adapted to maintain a certain amount of feed material on top of a molten inorganic bath, ensuring a substantially complete temperature gradient in the plasma arc furnace, thereby allowing for drying, pyrolysis and partial combustion of the SPL.
Furthermore, the embodiments described herein provide in another aspect a process, wherein the process requires only electricity as its energy source, i.e. no fossil fuels.
Furthermore, the embodiments described herein provide in another aspect a process for converting spent pot linings (SPL), comprising a plasma arc furnace that includes an anode and a cathode, the plasma arc furnace being adapted to gasify carbon to syngas and to convert a mineral fraction to vitrified slag, steam being provided to capture an excess energy from a gasification reaction and contributes to raise a syngas hydrogen content.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a cyclone provided at an outlet of the plasma arc furnace is adapted to collect dust particles.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a AlF3 reactor is adapted to convert hydrogen fluoride (HF) in the syngas to AlF3.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a waste heat boiler is provided for cooling down the syngas.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a baghouse is provided for recovering at least part of the dust particles not recovered by the cyclone.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a temperature of the plasma arc furnace is between 500° C. and 1800° C.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a vitrification of inert constituents of the SPL is carried out without requiring adding a slag agent, such as calcium oxide.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a conversion of HF to AlF3 is adapted to take place at a temperature higher than 500° C. but below 1000° C.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a source of Al2F3 to produce AlF3 is feed material to an aluminum electrolyser, purified Al2F3, or an intermediary aluminum hydroxide in a Bayer process.
Furthermore, the embodiments described herein provide in another aspect a process, wherein reaction heat produced by a neutralisation of HF by Al2F3 is adapted to produce more steam in a heat recovery boiler (for instance HX-0411).
Furthermore, the embodiments described herein provide in another aspect a process, wherein any excess heat from the gasification of SPL in the plasma arc furnace is adapted to be used for converting water vapor (steam) or liquid water to hydrogen.
Furthermore, the embodiments described herein provide in another aspect a process, wherein water is bled from a condensate-steam loop that flows in a waste heat recovery boiler (HX-0411).
Furthermore, the embodiments described herein provide in another aspect a process, wherein an oxidizing medium includes a mixture of air and water.
Furthermore, the embodiments described herein provide in another aspect a process, wherein a hydrogenation of fluorine volatized from the SPL is achieved via steam reaction.
Furthermore, the embodiments described herein provide in another aspect a process, wherein the slag can be valorized as a concrete additive.
Furthermore, the embodiments described herein provide in another aspect a process, wherein the plasma SPL gasification and vitrification furnace is adapted to maintain a certain amount of feed material on top of a molten inorganic bath, ensuring a substantially complete temperature gradient in the plasma arc furnace, thereby allowing for drying, pyrolysis and partial combustion of the SPL.
Furthermore, the embodiments described herein provide in another aspect a process, wherein the process requires only electricity as its energy source, i.e. no fossil fuels.
Furthermore, the embodiments described herein provide in another aspect an apparatus for converting spent pot linings (SPL), comprising a plasma arc furnace, an anode, a cathode, a crucible in the plasma arc furnace for receiving the SPL, the plasma arc furnace being adapted to generate an electric arc traveling from the anode to the cathode and within the SPL.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein the plasma arc furnace is adapted to gasify carbon to syngas and to convert a mineral fraction to vitrified slag, steam being provided to capture an excess energy from a gasification reaction and contributes to raise a syngas hydrogen content.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein a cyclone provided at an outlet of the plasma arc furnace is adapted to collect dust particles.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein a AlF3 reactor is adapted to convert hydrogen fluoride (HF) in the syngas to AlF3.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein a waste heat boiler is provided for cooling down the syngas.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein a baghouse is provided for recovering at least part of the dust particles not recovered by the cyclone.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein a temperature of the plasma arc furnace is between 500° C. and 1800° C.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein a vitrification of inert constituents of the SPL is carried out without requiring adding a slag agent, such as calcium oxide.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein a conversion of HF to AlF3 is adapted to take place at a temperature higher than 500° C. but below 1000° C.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein a source of Al2F3 to produce AlF3 is feed material to an aluminum electrolyser, purified Al2F3, or an intermediary aluminum hydroxide in a Bayer process.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein reaction heat produced by a neutralisation of HF by Al2F3 is adapted to produce more steam in a heat recovery boiler (for instance HX-0411).
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein any excess heat from the gasification of SPL in the plasma arc furnace is adapted to be used for converting water vapor (steam) or liquid water to hydrogen.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein water is bled from a condensate-steam loop that flows in a waste heat recovery boiler (HX-0411).
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein an oxidizing medium includes a mixture of air and water.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein a hydrogenation of fluorine volatized from the SPL is achieved via steam reaction.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein the slag can be valorized as a concrete additive.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein the plasma SPL gasification and vitrification furnace is adapted to maintain a certain amount of feed material on top of a molten inorganic bath, ensuring a substantially complete temperature gradient in the plasma arc furnace, thereby allowing for drying, pyrolysis and partial combustion of the SPL.
Furthermore, the embodiments described herein provide in another aspect an apparatus, wherein the apparatus requires only electricity as its energy source, i.e. no fossil fuels.
For a better understanding of the embodiments described herein and to show more clearly how they may be carried into effect, reference will now be made, by way of example only, to the accompanying drawings, which show at least one exemplary embodiment, and in which:
The new plasma technology described herein and using plasma provides a reliable solution to a problem afflicting the core aluminum manufacturing process.
The above overview of the two current alternative processes to landfilling stresses out what should be an optimal SPL treatment process. An optimal SPL treatment process would respond to four (4) major criteria.
These criteria are the following:
1. to generate a harmless solid by-product that can be easily discarded in any landfill.
2. to valorize the SPL carbon on-site for its energy content and thus to reduce the purchase of natural gas or other procured fuel.
3. to recover the SPL fluoride value for reuse on-site, without the need to comply with external regulations and without the need to buy a reagent to capture fluoride (such as calcium oxide).
4. to be a continuous process occupying a small footprint on the smelter site.
The fluorine recovery, as a valuable by-product reusable on-site, is key in the optimal SPL treatment process. Not all plasma technologies would deliver on fluorine recovery. For instance, some technologies trap the fluorine in their residual solid by-product via reaction with the reagent calcium oxide11. This approach requires the mixing of SPL with neutralisation and fluxing reagents as a first step to their process. The ratio of added reagents to SPL can be as high as 50%.
The thermal destruction of waste via plasma described herein responds to these four (4) criteria and does not need outsourced fluxing agents nor neutralisation reagents.
Therefore, as shown in
The furnace F gasifies the carbon content of the SPL 14 and produces a well-balanced syngas 20. The gasification takes place due to the controlled intake of air 22 and steam 24 to the furnace F. Gasification is the process of converting carbonaceous matter into a gaseous mixture of carbon monoxide (CO) and hydrogen (H2). The gasification reaction liberates a significant amount of energy. Steam captures this excess energy, provides part of the oxygen requirement for gasification and contributes to raise the syngas H2 content. Steam also contributes to the conversion of some SPL fluorides (NaF and Al2F3) into hydrogen fluoride.
The plasma process operates either in a continuous mode or in a semi-continuous mode. SPL 14 feeds into the furnace F continuously and syngas 20 continuously evolves from the furnace F. The slag 16, on the other hand, does not need to be poured out of the furnace continuously. The pouring of the slag 16 out of the furnace F can occur at a predetermined frequency, during which the feeding (of SPL 14, steam 24 and air 22) to the furnace F is idle.
As to the integration of the apparatus A and the plasma arc furnace F thereof into a complete SPL treatment process, the present apparatus A and its plasma arc furnace F greatly simplify the process of SPL decontamination, energy recovery, contaminant control and process integration within an aluminum smelter (see
Regarding the treatment of the syngas 20, in order to maintain robust and simple operations, the syngas treatment process is entirely dry from the feed inlet to the clean syngas delivery to the smelter. The major process units are an aluminum fluoride (ALF3) reactor 32, a syngas cooler 34 and a baghouse 36.
The following describes these three (3) major process units:
The AlF3 reactor 32 converts the hydrogen fluoride (HF) in the syngas 20 into a highly valuable by-product aluminum fluoride 38. The AlF3 reactor 32 uses alumina (Al2O3) as reagent, which is the raw material to any aluminum smelter. Such reactors are available commercially to produce AlF3.
The waste heat boiler (syngas cooler) 34 cools down the temperature of the syngas 20 from about 850° C. to 150° C. and by doing so, produces steam 42. The steam 42 is used for energy recovery and, for instance, to vaporize process water into the furnace F. Alternatively, the steam 42 can also feed a non-condensing steam turbine to generate electricity.
The baghouse 36 recovers any dust particles that neither a cyclone 44 at the outlet of the furnace F nor the AlF3 reactor 32 could capture. The baghouse uses regular particle bags to capture the dust. The dry syngas has a very low dew point. Thus, the syngas flowing through the baghouse is not prone to condensation.
It is noted that the flowsheet of
While the above description provides examples of the embodiments, it will be appreciated that some features and/or functions of the described embodiments are susceptible to modification without departing from the spirit and principles of operation of the described embodiments. Accordingly, what has been described above has been intended to be illustrative of the embodiments and non-limiting, and it will be understood by persons skilled in the art that other variants and modifications may be made without departing from the scope of the embodiments as defined in the claims appended hereto.
This application claims priority on U.S. Provisional Application No. 62/993,043, now pending, filed on Mar. 22, 2020, which is herein incorporated by reference.
Filing Document | Filing Date | Country | Kind |
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PCT/CA2021/050377 | 3/22/2021 | WO |
Number | Date | Country | |
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62993043 | Mar 2020 | US |