Mining Lithium from Spent Oil Wells – University of Alberta Talk by Professor Daniel Allesi

Introduction

In order to get to net zero emissions (or even to approach that goal), a great deal of energy storage will be required. That’s especially true in areas like Canada, which have long periods with little sunlight, thus making solar power infeasible for much of the year, unless ample electrical storage is available. Lithium is one of the materials that is needed for electric storage, so lithium is a strategic resource of great importance, one that is currently not that widely accessible in most of the world.

 

This talk about extracting lithium from brines associated with spent oil wells in Alberta, Canada was delivered by Dr. Daniel Allesi of the Department of Earth and Atmospheric Sciences at the University of Alberta, a specialist in geochemistry and geomicrobiology. It dealt with his team’s research into the development of processes to extract lithium at commercial scale and prices competitive with current supplies. The official name of the talk was “Electric Potential; Extracting Lithium from Waste in Alberta”.

Lithium Demand

• 
  Huge growth in demand is expected for lithium, especially for use in Lithium-ion batteries. Lithium is basically used in all parts of these batteries, the anode, cathode and solution.

   A 9X increase in demand is expected by 2030.

• But supply is having trouble keeping up, so a shortage is expected soon, by about 2025.

• Thus, many more sources of supply are needed, both conventional and unconventional.

• One of those unconventional sources could be brine from the Duveney Formation, an oil-bearing rock formation in Alberta.

• This brine is very salty, about 5X more than sea water (at about 136K ppm).

• However it also does contain a fairly decent amount of Lithium, averaging at about 55 ppm.

• Some cobalt, another strategic metal is also present, though at low concentrations.

Conventional Lithium Sources

• Currently, one of the main conventional source of supply are salt flats, which contain Li2CO3.

  • Solar evaporation is used to concentrate brine that has been collected in evaporation ponds. This results in a lithium precipitate, with a recovery rate of 50-60% of the lithium in the brine.

  • However, there are considerable environment impacts from this process. It uses a lot of water, in regions that are scarce in water. That water then becomes contaminated.

  • It also takes years to months for the necessary evaporation to occur and requires a lot of sunshine. These conditions are not that common (The dry high desert area of Chile is a current main source).
    

• Hard rock, open pit mining (granite pegmatite) is another conventional source of supply. This can produce both Li2CO3 and LiOH. There are various such mines around the world, either working or in development (e.g. Africa, Australia, U.S., Quebec, there is a possibility of an Alberta mine as well).

Alberta Lithium Potential

• Alberta has many millions of tons of Lithium Carbonate brine, in underground sources.

• Though these are relatively low grade sources compared to a lot of current conventional supplies, they are abundant.

• One estimate is 10 million tons at $25 thousand dollars per ton, so there is potentially lots of money to be made. Some brines have high grades, up to 140 ppm.

• They tend to be found in areas that have had extensive oil and gas production. Therefore, costs can be reduced as much of the infrastructure needed already exists (i.e. from the oil/gas exploration and development).

• Lithium in these brines is thought to be driven by hydro-thermal volcanic activity, deep underground.

  
  
  

Lithium Extraction Technology for Alberta Brine

• There are many options for lithium extraction, such as the use of solvents, membranes, electrolysis or selective absorption.

• The basic process can be thought of in these stages:

  • Drill and collect brine from underground source.

  • Use direct lithium extraction process (ion exchange) to remove lithium from the brine.

  • Re-inject the lithium-depleted brine back underground.

  • Do some cleanup, then precipitate solid lithium from the concentrate.

• Some technical details (very simplified)

  • Metal beads (the sorbent) are used to adsorb lithium ions from the brine. These are manganese (III) and manganese (IV).

  • The metals are dipped into the brine.

  • Essentially, lithium ions are adsorbed by being selected into small regions in the metal’s crystalline structure. That is due to its small size (lithium is only the third element in the periodic table).

  • This loads the metal beads with lithium.

  • The metal beads (sorbent) are then rinsed in a solution to extract the lithium from the sorbent, resulting in a highly concentrated brine.

  • Solid lithium is then precipitated out in ponds.

  • The sorbent is then dried out for re-use, to start the cycle over again.

• The process can be quick, on the scale of hours rather than months.

• It can recover 80%+ of the lithium, though there are also some other products produced by the process.

• Some technical/commercial issues to be worked out.

  • The big problem is the need to recycle and reuse the sorbent for the economics to be competitive (sorbent is expensive).

  • But, manganese is lost during the process, which is a problem as it is a key part of the sorbent.

  • Though the brine is from a “free site” (a site previously used for oil and thus has ready-built infrastructure) this creates a problem. The brine is often contaminated with hydrocarbons and other unwanted substances.

  • This coating of the sorbent with these oils may be part of the problem that leads to the loss of sorbent.

• This is the professor’s major area of research (i.e. the need to be able to reuse the sorbent).

  • For commercialization, the sorbent loss rate must be kept low, perhaps only 1% or so for each cycle of the process.

  • Basically, there is a need to “clean up” the brine in order to save the sorbent. This is especially true for organics in the brine.

  • One idea is to centrifuge the brine, to separate out the contaminants before mixing with the sorbent.

  • Washing with a surfactant (soap, basically) may help also help in the quest to maintain and reuse the sorbent.

  • Use of chlorine, peroxide or filtration (ultra fine, nano-level) are some possible approaches. But filters are expensive.

  • Coating the sorbent with something like zirconium might help to protect the manganese from reduction, so less loss of useful sorbent.

• H2S can also be a problem, by reducing Mn(IV) to Mn(III) or Mn(II), which are less useful sorbents. So that may need to be scrubbed.

Commercialization

• Problems have been solved in the lab, but can the process be done at a commercial, industrial scale? Research on this is ongoing.

• Using petrol-brine at a rate of 10K cubic meters per day, with a concentration of 80 ppm can yield 1500 tons of lithium per year.

• At current prices, that is feasible, but prices are high right now, so the economics might not work at lower prices.

• Economic incentives (e.g. tax breaks, subsidies) would be helpful (naturally).

• One advantage in favour of the process, is that the money earned via this method could offset oil industry water storage costs, so complete cost recovery may not be necessary (though always preferable).

• Another advantages is that a skilled workforce already exists in Alberta (oil/gas workers are already familiar with a lot of aspects of the overall process). Some incentives for re-training would also be useful.

• Ultimately, the greatest benefit would come from producing batteries from the lithium, rather than exporting it for others to do.

  
  

Sources:

The talk “Electric Potential; Extracting Lithium from Waste in Alberta”. By University of Alberta Talk by Professor Daniel Allesi

Alberta Brine Map and diagram: Eccles, D.R.; Berhane, H. Geological introduction to lithium-rich formation water withemphasis on the Fox Creek area of west-central Alberta (NTS 83F and 83K); Energy Resources Conservation Board, Edmonton, AB, 2011; pp 1-17.

Lithium Recovery from Hydraulic Fracturing Flowback and
Produced Water using a Manganese-Based Sorbent (Masters thesis byAdam John Seip

Wiki 

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