Join us for this week’s geohug session with Professor Jochen Kolb as he chats with us about the game-changing method of sourcing battery-grade lithium from geothermal brines. His group has developed techniques for selective lithium extraction and designed a pilot plant that is currently running in Germany. If everything works out successfully, there is reason to believe this method of lithium production could be scaled up – lithium-rich groundwater is not unique to Germany.
Come and join us this Wednesday 11th October 5 pm AEDT and let’s explore the science behind Professor Kolb’s innovative process, offering a clean, renewable, and efficient way to meet the surging demand for lithium in the clean energy revolution.
I am so happy to have Yan CB with us today so Johan holds the chair of geochemistry and economic geology at The Institute of Applied geosciences at k k Rua Institute of Technology in Germany he is the dean of studies uh for seven geoscience degree programs he has more
Than 25 years experience in economic geology research with a strong focus on orogenic gold deposits but since 2016 he has been working on the geochemistry of geothermal Brands and on aborption based metal extraction Technologies so his group have developed techniques for Selective lithium extraction and designed a pilot plant that is currently
Running in Germany so it is going to be wonderful hearing from him today all about this with lithium in geothermal and oil filled brins a new resource and its potential so it’s going to be a great session please keep using the chat we’ll open up the floor at the end and
Thank you so so so much for joining it’s amazing having you yeah thank you very much so yeah welcome thank you very much Jessica for for the introduction um so I will try to give you a little bit of an overview of our research here in CS I
Think the first slides I can uh get over very fast because you’re all aware of this uh that uh lithium is important becoming increasingly important and this is mainly because of the battery use mainly because of the electric cars I just bought one myself so they contain
12 kilos of lithium um instead of car before that had no lithium and we see that uh a lot of um predictions from different kind of institutes say we need uh whatever three to 13 or even more percent more lithium in the future than today and we have some leading companies
There’s aler and in Australia we have mineral resources limited dealing with with the lithium and then some Chinese and the Chilean companies and they mine uh conventionally either the solar here in South America or China or the spine from pegmatite or granite in Australia China mainly recently um we looked at um this
Geothermal water mainly here in Europe This Cornwall and then the uh upper Rin Valley where I sit uh at the moment um there’s something in Africa as well and New Zealand as well and of course salt and sea where we have considerable amount of lithium dissolved in the
Geothermal Waters and uh looking into to make this a real resource to be used is that a New Concept not at all right we know from Champagne pool and New Zealand and the geothermal power plants there that they are precipitates they contain gold they contain copper uh in New
Zealand they are all also mined for some of these um elements but it started already very very early in lello in Italy in Europe where already 1818 there was borax production from a spring hot spring like this and actually the power generation from this hot water only started in 1904
So we actually started using the brins for raw materials and then later the energy uh was used from these Waters almost a century later so I’m not sure how how familiar you are with geothermal power plants how they um set up here in in Europe in general
You have two Wells uh very often more than than two but but uh you basically have wells that are the production Wells and then you have discharge or injection Wells into your hot formation water Horizon you produce the water you go through a heat exchanger through a
Generator sometimes you have only one of those uh and then the water is discharged back into the subsurface to make sort of a cycle here and our idea was to to have lithium processing here to set up a yeah sort of a flow reactor where you can use
Different kind of technologies that we test to extract the lithium produce a lithium chloride that then can be processed into battery great lithium carbonate or lithium hydroxide since we have lithium chloride you can do either or it’s doesn’t really make a big difference and this technology should exist because it’s basically the same
That you do for the saell brins of South America right we want to go here because here when we produce the brine we have something here in Central Europe we have something between 120 to 180° cus and then after heat exchanging we have something between 60 and 80° celus and we thought
We could handle that better than the the hot temperatures so that is sort of a little bit the framework and that’s not very much different to oil fields right you have a production well you have a uh you have other walls where you can re-inject
Some oil fields do that some do it not and then you can put if it’s hot enough water you can put this or you can leave it out out and then you can hear when the metals currently we look into the geochemistry of these Waters and try to
Identify what other metals we would uh win because there’s not only lithium but there’s a bunch of metals I listed them here uh that are dissolved here um sometimes we have Rare Earth elements we have uh Boron phosphor phosphorus as oxides so there is quite some potential
In these but uh I think nobody would start to get iron out of these that would be stupid I think so the economic potential I would see more on these uh elements that have a low volume on the World Market maybe cesium rubidium um stonum or something like
That Cobalt maybe that have a high environmental footprint in mining and that have and that is very important in in Europe now a high criticality or vulnerability because here in Europe we don’t have so much plastical Hard Rock Mining and we look into this kind of uh Alternatives because we are highly
Populated area and we cannot afford so many open pits in our uh countries so let’s have a brief look uh into other areas to to show you the potential I think this is something that only comes up there’s not so much data around in the world when you look at Northern
America there um is a um data base and only 1% of 2,000 samples from geothermal fluids show lithium contents that are larger than 20 milligrams per kilogram so that is um something that uh shows you that that we also have to look for the right places to uh to get really
Lithium enriched Brines one of them would be Sal and C here in California um they have an average lithium content of 200 milligrams per liter um and there are different power plants that actually already run uh pilot and demonstrator projects in the area the other one would be smack over
Aransas which was mined for Bromine or is been mined for Bromine since 1957 s and they have an AUM content of 400 migs per liter in the brins and they are also looking into different technology so we’re starting in looking into these things also in Europe you see here a map
Of Europe I’m sitting here where all these dots are so it is a little bit of a hot area and this upper Rin grain um here very closely the southwestern German molasa Basin also the north German Basin so there’s quite a lot going on here in terms of geothermal
Energy generation because uh you might have noticed in the news that that Germany bans nuclear power and power from coal uh now so we need to have Alternatives and we look into this geothermal energy as well and get more and more data on the lithium content and
See that there is quite a lot here in in the German basins there is in Cornwall there’s activities here and uh we also see that there’s Italy which has considerable amounts of lithium in their fluids so when we look a little bit closer into Germany this is a heat map
On on the uh left hand side with a temperature sorry that it’s in German but you get it I think in at 3,000 M depth so we have here in this upper Rin grain I sit here exactly at this corner to to the um to France we have this
Upper rine grain with these anomalously hot temperatures at 3,000 mes depth um and this is where geothermal energy generation started somewhere in the early 2000s and we have this uh South German molasa Basin which I showed you before um we have quite high temperatures that are good for um for geothermal energy
Generation we have blow solidity which makes things easier uh in terms of corrosion and scaling processes the lithium content is locally quite High we don’t really understand yet how the distribution is then we have the upper rine grain um high temperatures here we have high salinity so the fluids normally
Have something between four to five times seawater the linity high lithium content then the north German Basin here here would be Berlin somewhere um that uh we have also have in some areas actually quite High lithium concentrations and then the Rin Ru where we have the relatively low temperatures
Very often also low lithium contents so that will be less prospective for lithium in geothermal BRS but shows you there are some areas in Germany that actually show some good indication of lithium in these geothermal BR the upper Rin grain structure is shown here where we have young sediments
In this structure which is about uh 40 kilm uh wide and uh 3400 kilometers long here’s Frankfurt here’s Basel and Switzerland um the so Switzerland would be here in the South this is France already here to the west and Germany would be the rest we have some um some higher mountains this
Is ver Riskin Origins Black Forest here uh and then the boundary Falls um and the Ryan River passing through here and then through the higher mountains here in this area so the uh the off or the the grabon that is around um a subsidence of around 3,000 M here in since the Cretaceous
Time and what you see is a distribution here with the red dots of different uh geometric um symbols you see the different occurrences of hot Waters so we know already since long times the Romans and the Kels already used that we have hot springs and there are quite a
Lot of resource some may know bon bon which is an Old Mundane U Resort all the Russians have been there all the time they like it for some reason um so there are hot springs there are and there are these geothermal power plants here in Germany these three
Just north of K which is here and then there are some in France and some one here in the South and there are companies active here in the area that is W energy resources that’s actually an Australian company that does exploration in the area they have 10 exploration licenses
And they bought uh this uh geothermal power plant here and they have an off-take agreement for the brine for this power plant here and they say that they have 26.6 million ton Li ium carbonate equivalent uh as resources in their uh 10 license areas um enbw that is the local energy
Producer here in in the area um they run this power plant and they partly they are part of these two French ones uh they say that they can win around 900 tons lithium carbonate equivalent per year in 30 to 40 years so they haven’t really um established the size of their
Reservoir cannot come up with with resource um estimates and that actually is also a difficult thing which we may want to discuss later what uh we say here at the moment with the current setup uh we need I said to start with we have around 12 kg in the our cars we
Need one hour production to get these 12 kg of lithium for for a car for example and if we take all four German um power plants we have a production of around six * 10 by six cuic meters a year of geothermal Waters and you can calculate that yourself with 150
Milligrams per liter or something like that um we get quite a significant lithium production which is 1% of the Global Production from 2021 so it’s it’s not insignificant what uh what is here it’s not super big but it could make a significant share to the German automobile industry which has to shift
To um e Vehicles now and there are considerable plans for battery factories also in Germany that would need the resources you see here um it’s maybe a little bit difficult to see these are the maps that I can get here’s car here car is here um and you see here the Ry
River and all these colored things are the the license area so there is on this side here uh of the Rin River there’s a lot of activity there appears to be less here but I think it’s it’s incomplete this is not up to date because a lot of
The area is taken by different companies now looking four resources of lithium in geothermal brins even Daimler who has a has a factory here a Lori Factory here they look into getting lithium out of that and heating their Factory with geothermal energy so what do we have here again a
Scheme on the left hand side of the upper rine Valley Frankfurt is here Basel is here caror is here and you see here some isol lines which show we have higher temperatures here in this in this area some colder temperatures um in other parts and this is a cross-section
Where we have the the crystalline verisk basement here and then all the sedimentary infill from tric to quinary sediments um quite faulted part so what we have here is fed granitic rocks Nies and then on top of that we have red sandstones of the lower Trias of The Bu
Sunstein um here in this part and that is overlay by by different other units which which seal this this uh lower part these are traces of fluids that are interpreted in the um since 2015 but this uh these two author that looked into the chemistry and say okay
We get some topographically driven fluid flow into the system and these are the hot brins here that are now produced here from depth between 2,500 and 5,000 uh meters uh by drills in into these um Horizons and uh we are just do starting new research on this and this maybe as
You might have uh figured out maybe too simplistic and we see a lot more diff different difficult things so when we look at the enbw power plant in BR we have two-phase flow which we can see here so we have a liquid and the CO2 Rich gas what are the major elements we
Are dealing with the sodium potassium calcium and chlorine I mean most of the solutes are uh sodium chlorides so that that is most of it and then we go into the minor elements we already get into lithium and other elements or n ions and then also already
When we go into the trace elements we see that there are elements like Arsenic and lead and cadmium that might actually make problems terms of health safety and environment and I come back to that that is a little bit the challenge here for the geothermal brins in the upper right
Bar here again composition on the left hand side you see these classical diagrams how we like to plot the the major elements so it’s chlorine dominated Waters it’s sodium potassium dominated Waters some are a little bit different to the South but I don’t want to talk about those too much so these
Are the main uh major fluids we put here some of the elements normalized to seawat because we thought I mean if we have elements that are at seawater level or below sea water we would be stupid to try to win them from geothermal brins so they should have some kind of elevation above
Seawater and you see that we have some of the Alkali and Earth Alkali elements um that are actually that is lithium we have uh cesium with a peak here we have barium with a peak then we have some elements in those brins so we have to be
A little bit careful because we have all the tubing and the wells and and all these kind of things that may um where we have iron or steel or kind of Steel things inside that would provide us with iron copper nickel um because these fluids are very corrosive and we get some of
These elements into the fluids and then we have here some others lead and uranium that are enriched in these fluid so we are at the moment uh one of my PhD students is getting all the data from the upper rine Valley so there is no database we start
To sample all of the brins that we can get hand on in terms coming back to lithium in terms of the lithium what do we have um uh you might have EXP expected that lithium correlates well with the chloride content so the more saline the fluids the more water the more lithium
Is in there and as opposed to many other basins um the upper R grain is difficult here we have the logarithmic value of the total dissolved solids TDS so all the solids that are dissolved um at the depth here from surface to 3,000 M and
You see that there is not a real Trend and in very many Basin you have a stratified um situation for the fluids so they start to decrease tend to decrease in solidity from the bottom to the top and that’s not the case in the upper Rin Valley what we interpret that
We have compartments that are sealed by aquitar so the reservoirs are not connected very often so we have difficulties here in identifying the reservoir size of our um lithium in the BRS when we look at the Isotopes they plot well all the Springs plot well on the meteoric water line
Here for Delta D Delta 18 o so they are at least mixed with meteoric water they have typical meteoric water signature here are two grinds from geother Thal power plants here you see that they are off that line so there is some mixing or some reaction going on with these brins
During their history when we look into chlorine bromine versus chlorine um chlorine bromine ratios versus chlorine contents we see also that the different um samples plot at different um locations in this diagram so there are some that have characteristics of having dissolved tertiary Haight there are some evaporates in the tertiary in
The grain so they have dissolved those uh then we have seawat composition around here and we see that’s quite a lot plot around seawater also these two from the geothermal power plants um but one more plots into the evaporation uh field and the other one more put plots into the halight
Disolution field so we have to do further studies to better understand what actually happened here to the fluids one other thing that we did was uh yeah some geochemical play around right medium cesium ratios versus cium content we do that because we can identify interaction with clay minerals
So this here would indicate interaction with Clay minerals in the subsurface this field would indicate equilibrium uh during alteration with the host Rock and uh this would indicate interaction with the crystalline basement rock of the briskin and also here you see they plot around this value of two where we are not
Really sure whether there was equilibrium or interaction with only some interaction with the with the w rocks this is important to know because we want to understand as for any um or deposit where does the water come from and where does the lithium come from we
Are only on the way to really understand that we have samples from one of the French geothermal power plants drill course from the reservoir this is suu uh close to car and we see different kind of alteration we see chloritization of biotite uh and uh other ferromagnesium silicates we see
Sitiation of the alkal Fel bars we see carbonate veining um yeah muscoid serde formation at different uh um grades and if you look into uh how it looks like we have a fresh Granite normally um that is not interacted with the with the brins and then we have in the reservoir we
Have highly altered rocks you see here there’s some serite here chloride here this is what you just saw the in the thin section photographs and what we did is we looked into these uh alteration projects with laser Elation icpms and we measured lithium content to understand whether these reactions would liberate lithium
Into the fluid and we have here Kel Spar altered Kel Spar PL CL and altered PL CL I made it simpler with with having this shading here which I hope you can see these are the orchard samples and these are the fresh samples so actually alteration of the Fel spars sort of
Catches lithium from the fluid from The Rock right so we have higher lithium values in the altered um minerals than in the fresh ones so F alteration does not liberalize lithium it takes up lithium from somewhere and this is not very surprising because um minerals like muscovite or Elite so they can
Incorporate lithium into their lce what else have we seen we have seen chloritization of biotite and here we actually see with the exception of one uh part which might be actually important we see that that chloride and biotite uh um don’t have significantly different values of lithium they have much higher
Values than than the felt bars but they don’t vary very very much what we did is the mass balance calculations and from that we see that this process actually liberates a little bit of lithium but we don’t know uh whether this is really enough to explain all the lithium in the
BRS we are a little bit pessimistic at the moment for this um scenario so what we do we see there’s another problem with the alteration we have this alteration of the granite in um two different stages what we see uh one is late magmatic Hunan stage where we have
Have magnetic materic aquous Carbonic fluids around 350° 2.2 kilobars and already here we see the biotite chloride transition right and we see sericitization of the F bars then we have a second hypogene alteration stage which is structurally controlled in the oltin and we have this done by meteoric
Fluids temperatures less than 200 de and again we get chloride elide oxyhydroxides here and this is much closer to the recent fluids which are aquous and have temperatures between 130 and 160° so we actually have a problem with the timing now we see this transition in our rocks in our thin
Sections we can measure liberation of lithium doing mass balance calculations but we don’t know whether this is super old uh in the biskin in the late biskin or something in the trey or something that happens recently okay so we do different analysis uh on drill cores um and there
Were colleagues who did experiments on powdered samples um so there is a possibility that the lithium comes from the interaction with rocks in the reservoir with the granitic rocks in the reservoir there are some people who think that this this is from evaporation of marine Waters but the stable isotopes
Doesn’t look like that so there is no way to make the stable isotopes match with a simple evaporation of sea waterer or it could be dissolution of evaporites there are several in the strata of the upper R grain so the basic answer is we still don’t really know where the
Lithium comes from also the geological setting right when we uh have it from the reservoir rocks then this would be R risking Gran ni or the red sandstones uh we had Marine Continental basins in the area so that could relate to um the lithium in the fluids or we
Have perum salts that could have reacted with Waters so we don’t really know what where we are at the moment still that’s good for a scientist right so we still have something to do okay when we look into making this lithium actually workable we have this power plant again production and
Reinjection and we have some challenges because in Germany we want to implement this lithium generation lithium mining if you want into this power plant we also want to have the heat and locally the electric power uh so we have to deal with these
126 or 60° huh on the hot side or on the cold side of the of the power plants we have to maintain a pressure of 22 bars here in B in this example but that’s that’s uh representative for all um the geothermal power plants here in the area
If we get too low temperatures or we if we release the pressures um we get scaling precipitation in our tubes which we have to avoid the flux in Bal is around 25 lit per second there are other plants where vcan energy is active they
Have 80 L per second so we have to deal with this uh flux I said we have a solute concentration this would be TDS the total dissolved solids of 120 gram per liter the complex chemistry as I shown uh quite some lithium the pH is
Between four and five and we have um gas I have shown you that before mainly CO2 so we have to deal with all this when we want to think about lithium processing getting the lithium out of these RS so uh from um I put here the EU view
In terms of research because here I have the overview I don’t have really the overview what is happening in the US and and other places potential exploration Technologies we are at still at the start start I said earlier that there are some pilot plants from demonstrators um and this is where we
Are we are doing research and we are following very very many different ways there’s electrolysis is one of the ways electrochemical pumping you see that there are universities involved liquid liquid extraction membranes um are researched and what we do because uh I have monologist in my group and I’m a minist
Myself we know a little bit about minerals and sorption and ion thieves and crystallography this is why we focus here on um on some of these sorption Technologies and we started with meanes oxides zeolites and lithium iron phosphates the the cathode material from from the batteries we skipped aluminium
Hydroxide and titanium oxide because they are groups from France that do research in this part so what we looked at was uh the literature their um Behavior Uh we have here in red that is the time for equilibrium so the time that is needed to get equilibrium in the sorption
Process and Q Max is how much lithium at maximum a milligram can be taken up for per gram of sorbent so you see here for maganese oxide for example that would be um um equilibrium after 24 hours and you have a maximum um of around 50 mgram lithium per gram manganese
Oxide you see it’s relatively fast for meanes oxide it takes a long time for t titanium oxide uh aluminium hydroxide appears to be a good candidate because goes fast and takes a lot of lithium iron phosphates zeolites here as Parts here with no data um that is uh shows
You where we are at the moment then again here all the possible sorbents with respect to the selectivity the selectivity is very important as I said because uh we pump the brine back into the subsurface and there are different regulations here in Europe in Germany and we are simply not allowed to
Modify the brine to a high extent so we are definitely not allowed to take out a significant part of the major elements otherwise we would not be allowed to uh put the brine back into the subsurface and that would sort of question the entire process here so we look into into
Selectivity in red is the lithium um and that is actually quite good for manganese oxide titanium oxides uh aluminium hydroxides iron phosphates and this is what we uh used to um to start our lab experiments uh we still wanted to try Clays and zeolites because they are common and cheap uh
Products so this is what we what we did right we uh ordered some of the material that we can get from the market and uh and these kind of things are used in water cleaning so we uh said okay let’s try those as well um we did some uh
Photographs with the sem so to characterize them they are all small particles uh that’s very important because the smaller the particle the higher the surface area and that is the the active area for the sorption process right so that is what we want um and what we did in our experiments is that
We uh did experiment uh batch experiments with 1 gram of sorbent uh 200 mL of lithium chlorine solution to start with and then some some milq water to rinse uh the system for kinetic experiments we use uh 200 PPM lithium buffered at pH sometimes we run unbuffered
Um reactions and we put in isotherms where we Vari the lithium concentration in uh in our reaction these are the basic uh principle that that we did we did this at different temperatures also at 60° celus as I said before this is the temperature that we uh think we will
Have on the co C side of the geothermal power plant so we run the experiment as these high temperatures we couldn’t run them at the pressure because that would have been too difficult in uh to to to yeah manage in the lab to work with high pressures so we tried clay minerals uh
They were very very difficult to handle because they were clogging everything and uh we get only a very very low Q Max for for lithium they have this super small grain size you see some of the experiments here that was really really hard to do and then we said okay this is
Nothing that we can scale up so we we skip this with the Clays we did Z lights here this in specific this Z Light 13x which you can uh buy we did uh here powders and Beads these are larger um um ball like things um that would be easier to implement later
Into larger scale systems powders we used mainly in the lab and we see okay we get quite a good Cube Max for the lithium at around uh 11 to 12 uh milligrams per gram and we see that that this uh have a nice isoterm here here which uh really
Shows you the the abortion characteristic not a big deal with the temperature so there appears not to be a big difference depending on the temperature we run those but the problem was that when we used the brine in the lab we saw that no lithium was taken up
This is the plot for lithium no lithium was taken up when there was calcium and potassium taken up from the from the brine so the Z L 13x as is is not selective enough so it would not be suitable and we skip that one so we have
Advantages it has a high stion capacity fast kinetics it’s cheap we can disorb with cheap acid again the math product uh the thing I wouldn’t give up too early we gave it up now for our study first but zes may be modified so we can increase maybe the
The selectivity to come over this major problem that other elements are preferred or lithium in a complex brine we started with iron phosphates uh which were promising from the literature very high maximum aborption capacity very high lithium selectivity uh and then when we did our first uh experiment that was really
Disappointing we had few Max of 1.22 mg per gram it was relatively fast after 30 minutes uh with the equilibrium but yeah you see the plot here that was not very encouraging but my PhD student she went on and looked a little bit deeper into
This and uh found out that we need some redox agent here in the system to actually disorb the lithium from the lithium iron phosphate um and we get quite a good lithium recovery with the with different agent nscl so sodium exchange doesn’t work alone very well so
We need this Redux U agents here to to do the um lithium work and we see also we measured iron and phosphorus with it so to to to monitor whether we destroy the sorbent during this desorption process and doesn’t appear to be the case so much so we ran the experiments now with
This and we find out that uh iron and phosphate they remain stable during the desorption and we can disorb the lithium from the lithium iron phosphate and we can also reverse the process the adsorption now also works with this uh redox agent um and we get
Up to 25 milligrams per gram uh out of the brins uh so this is a very very new result so this just came in last week uh and is very encouraging for these uh lfps so uh yeah it was early stage of research or it still is but now we produced the
First lithium from a geal brine using lfps which is uh quite encouraging because they are very selective and we have the experience from the battery research and there is it is possible that that we can simply take the the battery material uh from the end of life
Batteries to use them for our process so that these are options that that we look into at the moment yeah this is classical yeah if you want to like at school right you wet chemistry lab work with manganese oxide here um at the brins and the different things when we
Look into the manganese oxides which are widely used and I think most of the companies are relatively quiet about the processing technology so it’s really really hard to find out what they actually are doing or what they are developing but many I think in the US uh use manganese oxide based sorbents and
Here we have uh um the um Um um what is it called the the charge of the manganese uh and here the lithium manganese ratio and there are different lithium manganese oxide here we use lithium 1.6 manganese 1.64 because we can go into a redox reaction together with an ion exchange reaction here uh and this is
What we try to use in our system with the maganese oxide it’s a synthetic thing so we uh changed a bit the the the menu of making this lithium maganese oxide we start with hydrothermal and calcination processes and transfer first of all manganese oxide into lithium manganese oxide with
L M2 and then we have a further process to reach the tumet Tre that we want and to have these tunnels here in the structure the size of the lithium uh ion so that we get this ion SE effect this is how it looks like so we have these small little crystals they
They tend to Clump a little bit in the product but this is uh what it looks like in the electron microscope so small little things um that we can characterize by by xrd and um see how our synthesis works and uh it yeah worked not so well to start with
We still had some intermediate products and we had morph spaces in the product but then we optimized this and checked this always with the xrd and now we are happy that that some of these uh Peaks here disappeared um and we have a much better
Product so what is it all about we have here lithium oxygen manganese four manganese 3 and we have different positions of the lithium and we get the exchange between a proton and the lithium um here in different ways here with a bond that would be this path here uh that we just
Exchanged the H+ and the Li i+ and here when we have these interstitial lithium here then we uh do um the same thing but we also tend to have a redox uh process here which is shown here we get um lithium 4 plus u manganese 4 plus
To manganese 3 plus reactions um at different scales also here with the lithium exchange um and then that is a little bit problematic because when we do this further and reach manganes 2+ manganese 2+ will go into the solution and the the sent will be destroyed in the uh sorption desorption
Processes so we get some kind of alteration of the solent always and we have to minimize that so after two years in the lab we get into such nice so-called isotherms in the um uh where vary the lithium concentration against the lithium capacity and we see that we have very
High Q Max here at 31 milligrams lithium per gram sorbent but we have a plateau here at around 11 milligrams so that that is where we actually would work I think in the um in the industrial application we get almost everything out of the brain using the
The meanes uh oxide and it’s you see it’s a little bit complex that that is the the science behind it we have a multi-layer or Surface complexation um some precipitation of the tunnels or particle surface here these high uh values that that are a bit unusual because normally you have seen
That before you would get grass running like this and you wouldn’t get a peak like this okay so what about Kinetics I said that we have something between 25 L to 80 L per second so this will run up very fast to a lot of water so you want to have the reaction
Fast and that is actually working with the with manganese oxide we get uh 56% of the potential already within the first minute 65% after 5 minutes uh 75% after 50 minutes so that is a technical thing in engineering thing and economic thing then to adjust this um in the end
So we get very fast kinetics here also um dis option kinetics uh ignore the blue line below um here is the uh the uh lithium 1.6 maganese 1.64 we get very very fast dision as well and this is an hour so we get in the first minutes we get
A lot of the lithium dissolved again SB and stability I um showed you that there are maybe some reactions that that destroy the sorbent and we see that uh that this is actually happening here we have the repetition of desorption Cycles with using the same sorbent for
Recycling the sorbent all the time and we see that in the start we get quite some some maganese dissolution sometimes but this is reduced over time so the instable parts will will dissolve and there are stable paths that that would will remain and you see here the mass
That is lost that is uh maximum o 2% of the manganese is lost during a cycle so that is not very much the selectivity you have here on the right hand side with lithium so this brownish reddish part is the lithium part you see that most of the S
Material is lithium depending on the sent Mar uh if we only look at this upper part we see that also manganese is sbed yeah we don’t really care about it it’s part of the of the sorbent it actually might be good that this is sorbed as well may stabilize the entire
System and then we have here uh um yeah some calcium some potassium some sodium here in in the stion but this only a m very very minor amount this would be this small part here on top of it so we get uh very good um characteristics of this um as I shown
You good um stability good kinetics good aborption capacity but of course we have the fine grain size we are working with the powder it’s Redux sensitive so it will not work for strongly reduced uh brins and pH sensitive uh so most of our brins
Are around four to five to six so uh if we go higher with p uh yeah if you go higher with the pH that will be better and the sent is not commercially available so we have to uh make a facility to produce to synthesize the sbin from the manganese
Oxy what we did then after the successful lab experiments we went into upscaling and we built this this power plant uh this pilot plant at the buar power plant just 20 kilom North of cars we have two separate Cycles it’s a bit hard to see here the geothermal water
Comes in here is then run here this is the this is the cylinder uh where we let the geothermal water interact with the uh with the braine and that then goes around here we have a pump here so that can cycle the water here in the system
And on the other hand we have the dsorption so we bring a an 0.5 mol HCL that is uh less strong that the stuff that you take in the field for checking rocks um we put in here and cycle it here and then we get the lithium chloride
Solution here um out what we did is because we couldn’t really get the powder in into the system we made larger particles um into the system and as expected we have the lithium absorption capacity here uh it decreased very much with these larger particles so that
Would be the uh The Next Step actually to to really study how we can get uh this material inside the reaction vessel or part and have a high aborption capacity so we need the high surface area so we have to find some kind of way to put it
In there um but still it works so we get the lithium out uh of the brine also in this pilot plant and uh what we also see is that we s a little bit of material to the surface we get uh a little bit of contamination but we’re not really sure
Whether this is aborption of the surface we have some dead volumes in the system so there might be some cross contamination so simple washing with with water already reduces this to a significant amount so this is another thing that we have to investigate a bit further another thing that we have to
Take care about is that there are some nasty things in these Waters uh there is uranium and you produce radium nucleid um here that is mainly radium 226 and Lead 210 and radium 228 the colors are repeated here this is the analysis from the stuff that you have seen before so
We have some uh radium 226 and lad 210 here that is the m Beal per gram for the different parts um so we get some accumulation here so this is First Step Second Step third step fourth step so it’s increasing a little bit over time and also the 228 radium here
Is increasing over the time so we accumulate that but still these values uh are not uh dangerous they are not relevant for having um safety around radiation so we have to a little bit be careful we need long-term testing whether this is really a linear or whether we get situation at
A certain point and what uh measures have to be taken uh then after this a very good thing is that the reactor shows no radioactive contamination so what do we see further for this uh we do this of course for this direct application into to the geothermal power plants here in uh in
Germany and France but uh and all these evaporation pwns in the Solar deposits we can avoid if this works because it works for lithium chlorine BRS right and you don’t have 80 lit per second and 120° and 20 bars so it should be easier actually could the apply this to Inu
Leing um we uh try to apply it already now in battery recycling into hydom meterological processes because the lithium always gets into the uh into the processing water um and we can clean water pollution as well and uh as shown we can do this for lithium but we can do
This also for other elements uh as well and we have here um also in my Institute we have environmental uh people looking to this and there is quite a lot of overlap um here in the Technologies that’s my group so these are the PhD students and the the post
Talks working uh with me on the uh uh on the topic so without them I couldn’t have shown you all these uh interesting things these two are the uh lab people right they stand in the lab for weeks and hours and uh uh actually designed the the power the the pilot
Plant that was built in my workshop at The Institute so uh we also get noticed you may know this person here it’s the German foreign minister so politicians get uh um attracted which is very good because as a geologist you normally don’t have five minutes with with a
Foreign minister of a country that was very nice so I want to thank you very much uh for your attention and I leave it with that