EP-4741050-A1 - CONTINUOUS PRODUCTION OF LITHIUM SULFIDE

EP4741050A1EP 4741050 A1EP4741050 A1EP 4741050A1EP-4741050-A1

Abstract

A system and method of continuously producing lithium sulfide from a lithium-bearing feedstock is disclosed. The method may include introducing a continuous feed of the lithium-bearing feedstock into a fluidized bed reactor along with a continuous feed of a reducing gas. The lithium-bearing feedstock may be converted into lithium sulfide in the fluidized bed reactor by reacting the lithium-bearing feedstock with a sulfur-bearing gas in the presence of a reducing atmosphere created by the reducing gas. The temperature of the fluidized bed reactor may be controlled to facilitate the conversion reaction, such as by injecting an oxygen-containing gas into the fluidized bed reactor to react exothermically with the reducing gas. The lithium-bearing feedstock may be lithium hydroxide. The reducing gas may be hydrogen, carbon monoxide, or a combination thereof. The sulfur-bearing gas may be hydrogen sulfide, which may be generated externally to or directly within the fluidized bed reactor.

Inventors

ECCLESTON, ERIC
WAGNER, ERIC STANLEY

Assignees

Technip Energies France

Dates

Publication Date: 20260513
Application Date: 20241112

Claims (14)

A method of producing lithium sulfide comprising: continuously introducing a lithium-bearing feedstock into a fluidized bed reactor; generating a reducing atmosphere in the fluidized bed reactor by continuously introducing a reducing gas into the fluidized bed reactor; controlling a temperature of the fluidized bed reactor by controllably injecting an oxygen-containing gas into the fluidized bed reactor such that the oxygen-containing gas reacts exothermically with the reducing gas; reacting the lithium-bearing feedstock with a sulfur-bearing gas within the reducing atmosphere in the fluidized bed reactor to thereby convert the lithium-bearing feedstock into lithium sulfide; and discharging the lithium sulfide from the fluidized bed reactor; optionally, wherein the temperature of the fluidized bed reactor is maintained between 450 °C and 600 °C.
The method of claim 1, wherein: the lithium-bearing feedstock is lithium hydroxide; and the reducing gas is hydrogen, carbon monoxide, or a combination of both.
The method of claim 1, wherein the sulfur bearing gas is gaseous hydrogen sulfide; optionally, wherein the gaseous hydrogen sulfide is generated externally to the fluidized bed reactor by combining liquid sulfur with hydrogen to form the gaseous hydrogen sulfide, and the gaseous hydrogen sulfide is continuously introduced into the fluidized bed reactor; and/or optionally, wherein the reducing gas is or includes hydrogen and the gaseous hydrogen sulfide is generated in the fluidized bed reactor by continuously introducing liquid sulfur into the fluidized bed reactor such that the liquid sulfur reacts with at least some of the hydrogen; and/or optionally, wherein the reducing gas is or includes hydrogen and the gaseous hydrogen sulfide is generated in the fluidized bed reactor by creating a mixture of solid sulfur and the lithium-bearing feedstock and continuously introducing the mixture into the fluidized bed reactor such that the solid sulfur in the mixture reacts with at least some of the hydrogen.
The method of claim 1, further comprising recovering lithium sulfide solids from a stream of exhaust gas discharged from the fluidized bed reactor and combining the lithium sulfide solids with the lithium sulfide discharged from the fluidized bed reactor.
The method of claim 1, further comprising recovering solid sulfur from a stream of exhaust gas discharged from the fluidized bed reactor and reusing the recovered solid sulfur to generate, at least in part, the sulfur-bearing gas.
The method of claim 1, further comprising recovering heat from a stream of exhaust gas discharged from the fluidized bed reactor and returning the recovered heat to the fluidized bed reactor via heating with the recovered heat, prior to introduction into the fluidized bed reactor, one or both of the lithium-bearing feedstock and the oxygen-containing gas.
A system for continuously producing lithium sulfide comprising: a fluidized bed reactor; a source of a lithium-bearing feedstock in communication with the fluidized bed reactor and usable to supply a continuous feed of the lithium-bearing feedstock to the fluidized bed reactor; a source of a reducing gas in communication with the fluidized bed reactor and usable to supply a continuous feed of the reducing gas to the fluidized bed reactor; an oxygen-containing gas injector associated with the fluidized bed reactor and configured to controllably inject an oxygen-containing gas into the fluidized bed reactor to control a temperature of the fluidized bed reactor via an exothermic reaction of the oxygen-containing gas with the reducing gas; a sulfur-bearing gas within the fluidized bed reactor; and wherein the fluidized bed reactor is configured to produce the lithium sulfide through a conversion reaction of the lithium-bearing feedstock with the sulfur-bearing gas within a reducing atmosphere in the fluidized bed reactor.
The system of claim 7, wherein: the lithium-bearing feedstock is lithium hydroxide; and the reducing gas is hydrogen, carbon monoxide, or a combination of both.
The system of claim 7, wherein the source of the reducing gas is a hydrogen generator configured to produce a mixture of hydrogen and carbon monoxide by steam heating natural gas in the presence of a catalyst.
The system of claim 7, wherein the sulfur-bearing gas is gaseous hydrogen sulfide.
The system of claim 10, further comprising a hydrogen sulfide generator in communication with the fluidized bed reactor, the hydrogen sulfide generator configured to produce liquid sulfur by melting solid sulfur and to combine the liquid sulfur with hydrogen to form the gaseous hydrogen sulfide for introduction into the fluidized bed reactor.
The system of claim 10, wherein: the reducing gas is or includes hydrogen; and a sulfur melter is in communication with the fluidized bed reactor and is configured to produce liquid sulfur by melting solid sulfur and to introduce the liquid sulfur into the fluidized bed reactor to form the gaseous hydrogen sulfide in the fluidized bed reactor through a reaction of the liquid sulfur with at least some of the hydrogen.
The system of claim 10, wherein: the reducing gas is or includes hydrogen; and a feed blender is in communication with the fluidized bed reactor, the feed blender configured to produce a mixture of solid sulfur and the lithium-bearing feedstock and to introduce the mixture into the fluidized bed reactor to form the gaseous hydrogen sulfide in the fluidized bed reactor through a reaction of the solid sulfur in the mixture with at least some of the hydrogen.
A reactant generation system for a continuous production lithium sulfide fluidized bed reactor comprising: a hydrogen generator in fluid communication with a natural gas source and a steam source, the hydrogen generator configured to generate hydrogen and carbon monoxide by using steam from the steam source to heat natural gas from the natural gas source in the presence of a catalyst; and a hydrogen sulfide generator in fluid communication with the fluidized bed reactor, the hydrogen generator, and the steam source, and arranged to receive solid sulfur from a solid sulfur source, a portion of the steam from the steam source, and a portion of the hydrogen generated by the hydrogen generator, the hydrogen sulfide generator configured to produce liquid sulfur by melting the solid sulfur using the steam and to continuously generate gaseous hydrogen sulfide for introduction into the fluidized bed reactor by reacting the liquid sulfur with the hydrogen from the hydrogen generator; optionally, wherein the hydrogen generator is further in fluid communication with the fluidized bed reactor to discharge hydrogen, carbon monoxide, or both, as a reducing gas into the fluidized bed reactor; and/or optionally, wherein the hydrogen sulfide generator is further arranged to receive, from a gas treatment and sulfur recovery unit, recycled solid sulfur recovered by the gas treatment and sulfur recovery unit from an exhaust gas stream of the fluidized bed reactor, and is configured to use at least some of the recycled solid sulfur to generate the gaseous hydrogen sulfide.

Description

Technical Field The present disclosure relates generally to producing lithium sulfide, and more particularly although not necessarily exclusively, to continuously producing lithium sulfide from a lithium-bearing feedstock. Background Lithium sulfide may be used in the manufacturing of lithium-sulfur batteries. There is a growing interest around the use of lithium-sulfur batteries as a power source at least because lithium-sulfur batteries have a significantly higher energy density than other types of lithium batteries. For example, lithium-sulfur batteries can store as much as three times more energy per unit weight than other types of lithium batteries. Lithium-sulfur batteries also offer less risk of overheating during charging or discharging cycles and thus, less risk of associated fire danger. Further, because lithium-sulfur batteries are also of lighter weight than other types of lithium batteries of comparable energy storage capacity, lithium-sulfur batteries may be particularly attractive as a power source for manned and unmanned aerial vehicles, as well as electric land vehicles. Summary As used below, any reference to a series of examples is to be understood as a reference to each of those examples disjunctively (e.g., "Examples 1-4" is to be understood as "Examples 1, 2, 3, or 4"). Example No. 1 is a method of producing lithium sulfide including continuously introducing a lithium-bearing feedstock into a fluidized bed reactor. The method also includes generating a reducing atmosphere in the fluidized bed reactor by continuously introducing a reducing gas into the fluidized bed reactor, and controlling a temperature of the fluidized bed reactor by controllably injecting an oxygen-containing gas into the fluidized bed reactor such that the oxygen-containing gas reacts exothermically with the reducing gas. The method additionally includes reacting the lithium-bearing feedstock with a sulfur-bearing gas within the reducing atmosphere in the fluidized bed reactor to thereby convert the lithium-bearing feedstock into lithium sulfide, and discharging the lithium sulfide from the fluidized bed reactor. Example No. 2 is Example No. 1, wherein the lithium-bearing feedstock is lithium hydroxide, and the reducing gas is hydrogen, carbon monoxide, or a combination of both. Example No. 3 is Example No. 1 or Example No. 2, wherein the sulfur bearing gas is gaseous hydrogen sulfide. Example No. 4 is Example No. 3, wherein the gaseous hydrogen sulfide is generated externally to the fluidized bed reactor by combining liquid sulfur with hydrogen to form the gaseous hydrogen sulfide, and the gaseous hydrogen sulfide is continuously introduced into the fluidized bed reactor. Example No. 5 is Example No. 3, wherein the reducing gas is or includes hydrogen and the gaseous hydrogen sulfide is generated in the fluidized bed reactor by continuously introducing liquid sulfur into the fluidized bed reactor such that the liquid sulfur reacts with at least some of the hydrogen. Example No. 6 is Example No. 3, wherein the reducing gas is or includes hydrogen and the gaseous hydrogen sulfide is generated in the fluidized bed reactor by creating a mixture of solid sulfur and the lithium-bearing feedstock and continuously introducing the mixture into the fluidized bed reactor such that the solid sulfur in the mixture reacts with at least some of the hydrogen. Example No. 7 is any of Example No. 1 to Example No. 6, further comprising recovering lithium sulfide solids from a stream of exhaust gas discharged from the fluidized bed reactor and combining the lithium sulfide solids with the lithium sulfide discharged from the fluidized bed reactor. Example No. 8 is any of Example No. 1 to Example No. 7, further comprising recovering solid sulfur from a stream of exhaust gas discharged from the fluidized bed reactor and reusing the recovered solid sulfur to generate, at least in part, the sulfur-bearing gas. Example No. 9 is any of Example No. 1 to Example No. 8, further comprising recovering heat from a stream of exhaust gas discharged from the fluidized bed reactor and returning the recovered heat to the fluidized bed reactor via heating with the recovered heat, prior to introduction into the fluidized bed reactor, one or both of the lithium-bearing feedstock and the oxygen-containing gas. Example No. 10 is any of Example No. 1 to Example No. 9, wherein the temperature of the fluidized bed reactor is maintained between 450 °C and 600 °C. Example No. 11 is a system for continuously producing lithium sulfide. The system includes a fluidized bed reactor, and a source of a lithium-bearing feedstock in communication with the fluidized bed reactor and usable to supply a continuous feed of the lithium-bearing feedstock to the fluidized bed reactor. The system also includes a source of a reducing gas in communication with the fluidized bed reactor and usable to supply a continuous feed of the reducing gas to the fluidized bed reactor. The syst