Boiling water to remove hardness

(That's water to the rest of us!) Beer is about 95% water, so if you want to discuss water treatment, filtering etc this is the place to do it!
mbrew
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Boiling water to remove hardness

Post by mbrew » Mon Feb 06, 2017 4:37 pm

Hi,

I'm trying to learn about water treatment, its not sinking in too quickly though, really struggling to get my head around it!!

Been playing around with Grahams treatment calculator & Brewers Friend & seem to get conflicting results so even more confused.

As I'm more of a practical person I thought I'd have a little experiment to see how boiling & decanting the water would effect the mash PH, did a mini mash of MO & a tiny amount of Black (TTL clone) just to see what the PH would be, ended up with a PH of 5.2.

This is from a recent water report from my supplier so will be going with this just to try & learn.

Calcium 92
Magnesium 8
Sodium 40
Chloride 80
Sulphate 76
Alkalinity 138 CaC03

As I understand it You can only remove a certain amount of the alkalinity by boiling & seeing as my alkalinity is way to high for a pale I cant understand why the mash PH was 5.2, I used small range strips to test & I know there not the most accurate but surely there not that far out?

Is it possible for me to mash a pale with this water after boiling & have a good PH level?

I was about to give it a go but then read a lot of the calcium would be removed when boiling making it to low, could I just add Gypsum & to the mash & get somewhere near enough to make a reasonable brew?

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Re: Boiling water to remove hardness

Post by Eric » Mon Feb 06, 2017 6:39 pm

I too would be surprised with 5.2 mash pH after just boiling with a small amount of black malt in the mash. Crystal malt might have a greater influence.

Certainly if you can drop out some of that alkalinity it would help with your pale beers, but as you observe it would introduce other problems such as not knowing what your water then contained.

Boiling is costly, takes time to allow calcium carbonate to deposit and then decant All heat is lost and carbon dioxide can be absorbed to reintroduce some of the alkalinity.

What you have is ideal for acid treatment which is very easy by comparison.
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Re: Boiling water to remove hardness

Post by mbrew » Mon Feb 06, 2017 6:52 pm

Thanks,

I was thinking AMS would lower it & add sulphate / chloride which I guess is no bad thing for this beer style according to the calculators I have been playing with.
GW's calculator suggests AMS / CRS + Gypsum & CC.

I got the strips from the Malt miller, can they be that far out?

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Re: Boiling water to remove hardness

Post by Eric » Mon Feb 06, 2017 8:13 pm

AMS is probably your best choice initially for ease as it is available from many honebrew suppliers as CRS. I work on the basis that 1ml will reduce alkalinity by 183mg as CaCO3 meaning that 0.6ml of AMS in each litre of brewing liquor would reduce its alkalinity to about 28mg/l as CaCO3 which would be suitable for an all pale mash at 2.5l/kg with at least 100ppm calcium. CRS would then have increased sulphate by about 53 and chloride by 39mg/l assuming that half the alkalinity is neutralised by each acid, sulphuric and hydrochloric.

I used strips to measure pH for years. Those were obtained for me by a pharmacist friend and were accurate enough for brewing. They were very expensive and eventually wasn't able to obtain them, but by then a pH meter was less money than my previous 100 strips. I've not used those from the Malt Miller but they may be the best of the bunch now available. Others that I've tried in recent times worked well enough in clear liquid but were impossible to interpret in most worts.

To be totally honest, if you are able to accurately adjust your alkalinity with acid to suit your chosen grist checked using a Salifert kit, as well as ensuring your liquor contains sufficient calcium to protect the enzymes, to deposit oxalates, stops mash pH rising too high as you sparge and yet have enough left to enable your copper finings to work as they can, pH will be in the right region at every stage.

In time source yourself some hydrochloric and sulphuric acids as individual acids will be a lot cheaper and more versatile.
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Re: Boiling water to remove hardness

Post by mbrew » Tue Feb 07, 2017 7:28 pm

I was thinking about trying CRS but was a bit worried about using it while not fully understanding the process, this is why I thought I would give boiling a go.
When the strip showed a suitable PH in the mash I was a bit surprised going by what I had read & seen on calculators, for example Brewers friend said it should have been about 5.7. I don't quite understand the working of the GW calculator on here as to seems to assume a big reduction by boiling?

Would you say for my water CRS is the best option for me at the moment for all beer types? Get the alkalinity / mash PH right & don't worry to much about the rest for now, just want to make some decent beers before trying to get to involved.

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Re: Boiling water to remove hardness

Post by Eric » Tue Feb 07, 2017 10:23 pm

Graham Wheeler boils his water to reduce alkalinity, it works with his but doesn't work with mine. Mine has significant alkalinity associated with magnesium which doesn't deposit after boiling. I would expect boiling your water would be quite effective provided care was taken to let the alkalinity sediment and rack off the liquor, but then you would likely want to add back more calcium salts which if in the form of gypsum might not readily dissolve. There's nothing to stop you trying that approach.

There's nothing mystical about CRS, just a mix of sulphuric and hydrochloric acids in proportions that each acid neutralise similar amounts of alkalinity. As long as you don't use more acid than would neutralise all the alkalinity present, no acid will remain and the reduction in alkalinity is balanced by increased sulphate and chloride, all other ions remain unchanged. Sulphate has a drying effect on perception of taste while chloride improves perception of fullness (body) of palate such that hoppy beers benefit from sulphate while malty beers benefit from chloride. Using a Salifert kit you would measure alkalinity to determine how much of it needs neutralising and from that determine the amount of acid needed. A further test would confirm the actual alkalinity and from this could be calculated the increase in sulphate and chloride by assuming a reduction of 100ppm alkalinity as CaCO3 would result in 48mg/l increase in sulphate and 35.5mg/l increase in chloride, or pro rata.

With a low alkalinity needed for a pale malt grist you would have something like 130mg/l sulphate and 120mg/l chloride in your CRS treated liquor and you might want to double the sulphate. Roughly 56% of gypsum is sulphate and 23% is calcium, the rest water. So for an extra 130mg/l sulphate you would need 130/0.56 mg/l, that is 232mg of gypsum per litre to your acid treated water. That in turn would increase calcium by 0.23 X 232mg/l or 53mg/l to 145mg/l which is not a bad stating point.

For a darker beers a higher level of alkalinity is needed, so less acid would be required resulting in lower levels of sulphate and chloride. You would likely want to increase chloride to maybe get twice the level of sulphate present. Calcium chloride (dihydrate) is about 48% chloride and 27% calcium. In this case you would likely use around 200mg calcium chloride flake per litre of water used.

All this has been rough and ready, but there is no perfect or absolute water, but making good beers will likely spur one on to further research and further trials, the object being further improvements.
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Re: Boiling water to remove hardness

Post by mbrew » Tue Feb 07, 2017 10:56 pm

Thanks Eric,

I left the water in the kettle for over a day before decanting & was surprised by the amount of Calcium? I collected from the bottom & sides after it had dried out, certainly removed a lot but not all for the good.
I'm going to order some CRS and a Salifert kit I think & do it this way, seems more controlled & repeatable.
Might get one of those cheapy PH meters aswell, as long as they calibrate in the solotion they seem to work OK from what I can find out & not a big deal if it needs replacing each year at such a low price.

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Re: Boiling water to remove hardness

Post by Fil » Wed Feb 08, 2017 1:14 am

I will admit my brief looks at water chemistry have left me a little baffled, and have been bookmarked to return to one day ... However my own water being quite hard does also contain a fair degree of temporary hardness which exhibits itself as the scum on well brewed tea, And when i give my hlt liquor a 15-20 minute boil I will also exhibit a chalky dry skin to the liquor surface which i draw off from below when its cooled back down to pitching temps.

So i would suggest that unless you also notice scum islands on well brewed tea, then perhaps the hlt liquor boil would be of little benefit.
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Re: Boiling water to remove hardness

Post by Eric » Wed Feb 08, 2017 4:46 pm

While boiling will reduce alkalinity, it's an imprecise method compared to acid treatment. More, it is expensive and timetaking.

You don't need to be a chemist to brew, just the services of good one to determine what a sample of your water contains. Without that there is no known starting point.

On a brew day it is wise to check that your water hasn't changed composition from when it was tested and if it has, by what amount that you might compensate.

A Salifert kit costs less than £10 and will last 2 and more years. It can measure alkalinity before and after any necessary treatment and show any change in your water.

A TDS meter costs £5, measures conductivity to display that as Total Dissolved Solids in mg/l assuming all solids are common salt. While with different electrical conductivity that weight won't be of the specific ions in your water, it will, for most, in seconds show any change in your water supply and by what proportion.


My water varies significantly, TDS mostly 540ppm, but after heavy rain reduces by dilution. Last year TDS on brew days ranged from 240 to 540ppm. Most will not suffer to this extent, but because I do, WallyBrew analysed several samples. That showed, for practical purposes, a linear relationship between TDS and major ions.

I have a range of foodsafe acids for liquor treatment, but mostly use sulphuric and/or hydrochloric, the former usually for pale and certain hoppy beers and the latter for stouts and milds. They are diluted so that 1ml of either will neutralise 300mg of calcium carbonate. A TDS reading enables me to approximate the alkalinity present in a moment, provided the water and meter are at the same temperature else it takes time for the reading to stabilise. Knowing the level of alkalinity as calcium carbonate, all that is necessary is to subtract the amount of alkalinity required to remain and to multiply that result by the volume of liquor needing to be treated. That gives the weight of calcium carbonate and knowing that 1ml of my acid neutralises 300mg, simple division will determine the amount of acid needed.

For an all pale grist I normally adjust alkalinity to 25mg/l as CaCO3, treating 24 litres from which the mash liquor would be drawn when heated. Assuming a TDS reading of 540, alkalinity would be 255mg/l as CaCO3 requiring a reduction of 230mg/l. So 24 litres with an excess of 230mg of alkalinity contains an excess of 5520mg as calcium carbonate. Therefore when using acid that 1ml will neutralise 300mg of CaCO3 requires 18.4ml.
The TDS measurement and calculation are done while the tap is running, the tricky bits are getting the meter and water sample to the same temperature and remembering to turn off the tap at the right point, but with practise they've been solved. I would then add most of the acid, stirring and allowing time for mixing, the reaction and any carbon dioxide to escape while weighing grains and what other tasks are required. A sample of liquor is then tested using the Salifert kit, 2 minutes at most as the alkalinity should be quite low and need little reagent, and the rest of the acid added when its need is confirmed.

Sparge liquor should be less alkaline than for the mash to avoid pH rising excessively as the sugars in the wort reduce and their buffering powers decease. I treat mine separately then add it to the remnant of that for the mash. Salts are the next for consideration to obtain the required calcium level at each stage and the sulphate and chloride levels in the finished beer.
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Re: Boiling water to remove hardness

Post by mbrew » Wed Feb 08, 2017 8:28 pm

A couple more questions,

When using Acid does it effect the flavour at all? I know the acid gets neutralised but what's left behind?

One of the other reasons that attracted me to boiling was the removal of Chlorine / Chloramine from the water, what are your thoughts on using Campden tablets or just leaving for a day or so to let it evaporate?

Anglian water say "Chlorine:
Disinfection is important to ensure there are no harmful organisms in the water. We use chlorine to disinfect drinking water supplies. No
ammonia is added in this process which means your water supply is not chloraminated."
Min Avg Max
Chlorine (free) No legal Limit mg/l 92 <0.05 <0.21 0.5 0
Chlorine (total) No legal Limit mg/l 74 <0.05 <0.47 0.85

I'm guessing I can get away without the use of more chemicals?

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Re: Boiling water to remove hardness

Post by Eric » Wed Feb 08, 2017 11:47 pm

The alkalinity in your water will mostly be in the form of calcium bicarbonate, maybe a little calcium hydroxide and similar in lesser proportion with magnesium. Any other alkaline compounds present can be for all practical purposes ignored. These are formed when rainfall and carbon dioxide in the atmosphere combine to form carbonic acid which then reacts with limestone.

Calcium bicarbonate reacts with sulphuric acid to produce calcium sulphate, water and carbon dioxide. There is no other residue.
Calcium sulphate is common in many waters, it comes from natural gypsum deposits, is used by brewers and is what made Burton upon Trent World famous for beer.
Alkalinity reduced to 25mg/l by sulphuric acid will add sulphate equivalent to the addition of 1 gm of gypsum into 5 litres of water which can hardly change its taste. It will have an influence on the perception of taste in the final beer which depends on preferrence.
Calcium bicarbonate reacts with hydrochloric acid to produce calcium chloride, water and carbon dioxide. There is no other residue.
Calcium chloride is a commonly used brewing salt with no taste I can discern at levels I've used. The most additional amount of chloride created is the equivalent of 1 gm of calcium chloride flake in 6 litres of water. Chloride increases fullness and malt flavours in beer.
I know some who only drink beer that's sufficiently cold to dull their tastebuds or has little flavour, whom I suspect mightn't care for such additions were they ever to brew.

Organic acids like citric, lactic, phosphoric do leave additional residues with flavour. For example only one third of phosphoric acid reacts with alkalinity, the unused two thirds passing through to the beer with its attendant buffering capacity keeping pH higher than it would otherwise be. Such acids can be used to good effect in waters with little alkalinity.

Chlorine in UK waters only rarely spoils beer. Use half a Campden Tablet in a 5 gallon brew until you forget when you will know the answer. I can't remember the last time I remembered, possibly 2 or 3 years ago.

I would advise the addition of some calcium salts, all my experience confirms this if you want a beer that clears quickly. Read particularly the last two paragraphs of Note 5 of Graham's Water Treatment Calculator. At 92ppm calcium your water has enough calcium but once it is used it is deposited. You need enough in the boiler to get hot break to form and deposit and for copper finings to work and you will make your initial tasks easier by making sure there is enough. Once your beer is better than what you can buy comes time to find out what happens with low levels of calcium. At least you will then know how to solve that problem when it arises.
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Re: Boiling water to remove hardness

Post by mbrew » Thu Feb 09, 2017 11:38 am

Thanks for explaining all this to me Eric, you've convinced me this is the way to go for now.
Salifert kit, CRS & some salts about to be ordered.

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Re: Boiling water to remove hardness

Post by k1100t » Thu Feb 09, 2017 12:25 pm

mbrew wrote:Thanks for explaining all this to me Eric, you've convinced me this is the way to go for now.
Salifert kit, CRS & some salts about to be ordered.
Make sure you also buy some scales that (claim to) do +/- 0.01g, if you don't already have any.

Cheers,

Bob.
I like beer --- Currently rebuilding the brewery, this time with stainless... --- http://beer.bobarnott.com/

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Re: Boiling water to remove hardness

Post by mbrew » Thu Feb 09, 2017 1:20 pm

Just having a bit of a play with GW's & BF calculators & getting some very different numbers for the amount of CR to be added.
Using my numbers from the first post & assuming 26l of liquor & a mash PH of 5.4 Brewers friend is coming up with 17.5ml in the mash & 9.5 for the sparge, GW is saying 15.9 for the total volume.
Am I missing something?

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Re: Boiling water to remove hardness

Post by Eric » Thu Feb 09, 2017 3:35 pm

mbrew wrote:Just having a bit of a play with GW's & BF calculators & getting some very different numbers for the amount of CR to be added.
Using my numbers from the first post & assuming 26l of liquor & a mash PH of 5.4 Brewers friend is coming up with 17.5ml in the mash & 9.5 for the sparge, GW is saying 15.9 for the total volume.
Am I missing something?
You intend to treat 26 litres of water with alkalinity of 138mg as CaCO3 per litre. That water therefore can for purposes of calculation be assumed to contain 3.588g calcium carbonate (26 x 0,138). As 1 ml of CRS/AMS can neutralise 183mg of CaCO3, 15.9ml would neutralise 2.91g (15.9 x 0.183) to leave 678mg and shared in 26 litres would reduce alkalinity to about 26mg/l as calcium carbonate.

I can't speak for the BF calculator, but suspect it is pH centric based on the findings in Kolbach's later work on mashing pale malts in very soft waters. 27ml of CRS has enough capacity to neutralise more than 4.9g of calcium carbonate, over 1.3g more than your water contains. That I can't explain.

What are you missing? May I suggest not using a pencil, paper and four function calculator?
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