Biopowered - vegetable oil and biodiesel forum

Biodiesel => Chemistry and process => Topic started by: B100 on November 08, 2021, 08:44:15 PM

Title: methanol too wet
Post by: B100 on November 08, 2021, 08:44:15 PM
Working with an IBC of methanol from my usual supplier, every batch is proving problematic.    My process uses KoH.  So tested the methanol SG and found the probable cause.   The SG of virgin methanol should be 0.791, but this IBC is 0.780.    I'm using a laboratory-grade hydrometer which has always been spot on with previous IBCs, so it looks like I've got a wet batch of methanol. 

There is a lot of info on the web about the consequences and problems caused by using wet methanol, but I can't find any advice on how to cope with it.   Any suggestions - apart from going back to the supplier (which I will try tomorrow) ?
Title: Re: methanol too wet
Post by: dgs on November 08, 2021, 10:03:31 PM
I'M not quite with you here. Surely if you had water in your methanol your sg would be higher not lower. I've use methanol containing 1% water and it doesn't give a significant yield reduction.

What are the problems you are finding. You can dry your potassium methoxide using quick lime (calcium oxide) its a bit of a mess about but it works really well if you do it correctly.
Title: Re: methanol too wet
Post by: B100 on November 08, 2021, 10:41:21 PM
If the SG should be higher with extra water content, what conclusion should I draw if the SG is lower than expected ?

The problem I have is that using "standard" quantities of methanol and KoH (which I have been using for 9 years), the conversion to bio and glycerine fails to take place.   I have to then run a second process using about 30% more methanol and KoH.  I have tried running the second process with 10% and 20% extra, but without success.   Nothing else in the overall process has changed.   The KoH is kept dry and the used vegetable oil is always dried using glycerine from the last process. 
Title: Re: methanol too wet
Post by: countrypaul on November 08, 2021, 11:12:36 PM
As Dave says, if your methanol has water in it the SG will increase. Can we assume that the SGs were measured at the same temperature and that temperature was what the hydrometer was calibrated at? If the SG of your methanol is lower it could be contaminated but I cant gues what with.

When you use 30% extra methanol and KOH do you end up with lots of extra soap (gylc)? Water catalyses the formation of soap so if the methanol had lots of water present we would expect more soap. I have used 97% methanol (3% water) and whilst I used NaOH the amont of soap was slightly higher but not worryingly so.

Can you check the acid value of your methanol? I don't know if you normally titrate your oil, but if so try titrating some methanol and let us know.

Can you try a Dr Pepper with 30% more KOH but the same amount of methanol?  Just wondering if the methanol could have methanoic acid (formic acid) present - though I have no idea what that would do to the SG - I would guess increase it.

Have you got any other KOH or NaOH - if so try a Dr Pepper with that and see if it works normally. You can buy 500g oh NaOH from a pound shop fairly easily if you want but check to make sure it is just NaOH.
Title: Re: methanol too wet
Post by: B100 on November 09, 2021, 11:26:46 AM
Wow.  I have just called my supplier and have discovered that I am not the first person to complain about their methanol.   They took responsibility straight away.  They are going to collect what's left in a couple of days and replace it ASAP.    I am impressed by their response, but I am out of pocket by quite a lot for wasted oil as the conversion rate has been reduced by 30%, and I have obviously used unnecessary electricity and KoH.   

Thanks for all your help in trying to troubleshoot this one.   Much appreciated. 
Title: Re: methanol too wet
Post by: dgs on November 09, 2021, 01:37:45 PM
Are we allowed to ask who the supplier is.
Title: Re: methanol too wet
Post by: DavidA on November 09, 2021, 04:42:59 PM
I notice that Isopropanol is .785 at 20 C

Any chance that you have a mixture of Methanol and Isopropanol ?

Could be why the supplier is so quick to change it.
Title: Re: methanol too wet
Post by: B100 on November 09, 2021, 05:43:20 PM
I was unable to find out what the contaminant might be, but they were certainly very quick to agree to replace the IBC.   The supplier was Bonnyman.     It will be interesting to see how they react when I ask for compensation.   The hassle this has caused has taken a lot of extra time as well as wasting feedstock (which is hard to come by in this area), KoH and electricity. 
Title: Re: methanol too wet
Post by: dgs on November 09, 2021, 06:24:01 PM
If It was IPA doesn't that work out at around 50% surely at that you would be able to smell that sweet aroma.
Title: Re: methanol too wet
Post by: B100 on November 09, 2021, 08:55:14 PM
As it happens, I just happen to have 5L of IPA that has only just been opened.   I will try the sniff test tomorrow in daylight to see if I can detect any in the methanol.   I can't say that I'm particularly optimistic as my sense of smell has become impaired over the years by too many curries. 
Title: Re: methanol too wet
Post by: nigelb on November 09, 2021, 10:40:18 PM
Ask for a C of C....a certificate of conformity for the batch you receive. Virgin methanol should be just that...virgin. I'll find out tomorrow from my boss to see if reclaimed also carries a potential c of c.
Title: Re: methanol too wet
Post by: B100 on November 09, 2021, 11:32:38 PM
My plan is simply to measure the SG from now on of any incoming IBC.   
Title: Re: methanol too wet
Post by: nigelb on November 10, 2021, 08:53:28 AM
For your own satisfaction do just that. My advice would be to ask for the certificate and complain the moment you think there is a problem with it. Suppliers have a duty of care and will respond quickly. Without being certain, and it is wise to ask questions of Bonnymans, but I beleive they are not manufacturers of methanol. Very much like ourselves. We buy ours in from Brentag or Tennants. We always ask for the conformity certificate.

Bonnymans may of knowingly or not knowingly supplied you with reclaimed methanol instead of virgin. You requesting a copy of the c of c will tell them you mean buisness.
 
Title: Re: methanol too wet
Post by: DavidA on November 10, 2021, 11:55:26 AM
If It was IPA doesn't that work out at around 50% surely at that you would be able to smell that sweet aroma.

It might be an idea to keep back a couple of Litres of the bad stuff as evidence.

Maybe use some of it for distillation tests if you feel so inclined.
Title: Re: methanol too wet
Post by: WesleyB on November 10, 2021, 05:30:32 PM
A fractional distillation aparatus could give you the boiling point of your  material or materials .   It would be some trouble .   If you took about 50 milliliters of the alcohol in a beaker then put a couple of grams of  sodium bicarbonate into it , then if bubbles are produced you've got water in it , not just alcohol . 
Title: Re: methanol too wet
Post by: Tony on November 10, 2021, 10:09:22 PM
You requesting a copy of the c of c will tell them you mean buisness.

That's a good tip to remember, and hopefully never have to use.  I guess you see this "from the other side" dealing with customers?

Whatever was the contaminant on that methanol can't have been water if the SG was lower - would be interesting to know what it was.  Was it bought as reclaimed methanol?

I've had some funky smelling reclaimed over the years but the SG has always been spot on.  The most problems I've had have been with KOH, getting some fresh stuff from Nige was a revelation when batches started going well again!
Title: Re: methanol too wet
Post by: B100 on November 12, 2021, 10:37:13 AM
The methanol was ordered as virgin.

When I asked today for a C of C for the IBC that was delivered in June, it was refused.   I was told that it had to be requested at the time of ordering.    Does this sound right ?   Can they refuse ?

 Obviously I have asked for a C of C for the replacement IBC that will arrive early next week.

Title: Re: methanol too wet
Post by: nigelb on November 12, 2021, 05:02:25 PM
They refused it because what they sold you wasn't virgin. The c of c will have the batch number on it and it should match the batch number on the IBC.
Title: Re: methanol too wet
Post by: B100 on November 12, 2021, 07:10:30 PM
They are going to provide me with a replacement IBC next week, so what are the benefits to me in pursuing a C of C ?     Or is this just an academic exercise with no effective value ?
Title: Re: methanol too wet
Post by: nigelb on November 12, 2021, 08:23:18 PM
A c of c for the stuff they are picking up? No value at all. With other clients having issues shows that it wasn't what they said it was. Some companies will try and get away with whatever they can to make a quick buck. Bottom line is they knew what they were dealing with. 

We get wind of reclaimed meth when large quantities come onto the market. We refuse to deal with it and only get virgin methanol into our unit.

All chemicals that come through our doors are traceable and accountable.....Bonnymans should be no different. Refusal of a c of c could imply they have something to hide.
Title: Re: methanol too wet
Post by: nigelb on November 15, 2021, 02:47:06 PM
My boss says you would be better to request a c of a. Certificate of analysis. It'll show everything thats in there. Time passed is not a good enough reason for refusal of any certification. Even reclaimed will be certificated.

Get a C of A rather than C of C.
Title: Re: methanol too wet
Post by: Julian on November 15, 2021, 05:53:39 PM
Nige ... could I have a C of A  for the barrel of methanol I collected at the BBB?

(Awaits reply with intrepidation)
Title: Re: methanol too wet
Post by: nigelb on November 15, 2021, 08:54:04 PM
No...too much time has passed!! 🙄....kidding😁

Can you let me know the batch number on the barrel. Should be a little white ticket.
Title: Re: methanol too wet
Post by: Julian on November 15, 2021, 11:55:19 PM
....kidding😁

Me too ... just checking.
Title: Re: methanol too wet
Post by: B100 on November 16, 2021, 08:17:13 PM
Clarks must be having a problem with driver shortages.   Bonnymans assured me that the contaminated IBC would be collected last friday.   Some hope.  I chased it on monday and was assured that somebody from the Barton le Clay depot would contact me, but nobody did.   A scottish chap from Clarks HQ later assured me that the collection would take place today (tuesday).  And it did.  Even better, the replacement IBC came at the same time.   I checked the SG when the sample has warmed up and it was spot on.     

Now I need to gather my thoughts and work out just how much to claim in compensation for wasted feedstock, wasted electricity and wasted KoH.   I will let you know their reaction. 
Title: Re: methanol too wet
Post by: B100 on November 19, 2021, 09:09:20 PM
My initial calculation of losses suggests that I've lost £210 worth of feedstock as the result of each batch produced being reduced in efficiency by a third.   I normally expect 140L of bio per batch, but using contaminated methanol has resulted in a large drop in output and more waste.    Electricity consumption has been increased because of at two extra processes per batch, and more KoH has been used, but these are minor issues by comparison with lost feedstock.

Apart from Bonnyman, where else can I buy an IBC of methanol ?    My previous IBC came from Sidwil, but they appear to be expensive at the moment.
Title: Re: methanol too wet
Post by: Keef on November 19, 2021, 10:20:44 PM
Sounds like Bonnyman have worked out more expensive than Sidwil to me  ;)
Title: Re: methanol too wet
Post by: B100 on November 20, 2021, 10:42:01 AM
In the short term, you are right.   But what about the next IBC ?   If I claim against Bonnyman for my losses, I think it possible that they might not sell to me again.   So then where do I go ?
Title: Re: methanol too wet
Post by: Keef on November 20, 2021, 11:39:19 AM
My initial calculation of losses suggests that I've lost £210 worth of feedstock as the result of each batch produced being reduced in efficiency by a third.   I normally expect 140L of bio per batch
Sounds like you've run a lot of batches before you queried it.
Even at 50p a litre, £210 is 420 litres wasted meaning you've processed 1260 litres!
Title: Re: methanol too wet
Post by: B100 on November 20, 2021, 12:38:12 PM
I should have suspected the methanol earlier, but I kept looking for the cause of the problem in other variables such as the quality of the oil, and how well I had dried it.   The KoH has also been sitting around for more than a year, getting damp in poly bags which are not fully sealed.    I'm kicking myself for having left it for so long before checking the methanol.
Title: Re: methanol too wet
Post by: Tony on November 22, 2021, 04:01:53 PM
Apart from Bonnyman, where else can I buy an IBC of methanol ?    My previous IBC came from Sidwil, but they appear to be expensive at the moment.

Barrettine in Bristol are easy to create an account with and friendly to homebrewers.  It has also been free delivery on orders over £300 previously, hopefully still applies.
Title: Re: methanol too wet
Post by: B100 on November 22, 2021, 07:36:19 PM
Great.  Thanks.   I will try them tomorrow.
Title: Re: methanol too wet
Post by: countrypaul on November 22, 2021, 08:34:51 PM
You could also ask Nigelb