Distillery Analysis

[bostonapothecary]

Hello all.

A very neglected thing in the new arm of the distilling industry is analysis. Lately, I'm trying to make my focus developing a pragmatic best bang for the buck distillery laboratory. I'm hoping to learn what people are currently practicing and what they would like to take on next, even if they're only growing from a hydrometer and pH meter upwards.

Lots of people are buying big ticket u-tube densitometers before they buy other tools like automatic titrators, but is that a good idea? One of my projects is trying to add pycnometry to my analysis tool set as a stepping stone before a u-tube densitometer. It is no walk in the park, but I'm getting there.

The big tool that is looking like the foundation for any distillery lab is Arroyo's birectifier lab still. It can tell us incredible things about spirits and allow us to intimately compare them. As far as time goes, when manually operated it can take 2.5 hours to operate and then perhaps 20 minutes to assess the output. Is that too long for many people's busy schedules? We are hoping with automation to dramatically slash the active time it takes to operate so it can run twice a day unattended. My consulting work is showing that it can significantly shorten product development time and expense for products like gin, paying for itself quite quickly. The birectifier also allows a priceless education in the inner workings of role models and competitors.

Is anyone currently using automatic titration? I'm looking at buying a model that is about $3500 from Hanna Instruments. I want to investigate the concept of Δ acidity for working with ferments that have large buffers. This is an idea first brought to my attention by Michel de Miniac in a French paper I translated. The Δ, as opposed to the pH, can imply how many acids beyond the norm of your yeast were created by bacteria. This can either be used to tell when clean spirits go dirty or perhaps when intentionally dirty products like heavy rums become a run away train. Within anyone's current experiences, would that tool pay for itself quickly? or are the learning curves of integrating the equipment another large barrier?

Is there any interest in other titrations such as for fusel oil or esters and has anyone priced them out? It is surprising me that ester obsessed people are not investing in counting esters or perhaps I'm just not aware of it. Some analysis such as ester contents seem like it can be woven into marketing.

Has anyone tried the exhaustive test which is a low cost rudimentary alternative to titration that works in a variety of scenarios? The Germans developed a variety of organoleptic techniques that seem really useful before shelling out the money for chemical analysis equipment.

Is anyone interested in botanical assay? I have the lost Seagram procedures that I haven't done much with. They cost about $3000-$4000 to fully implement (half of that is an analytical balance). The tools required can also help perform a bunch of other tasks such as measuring barrel solid obscuration by the TTB evaporation method. Seagram used two specialty pieces of lab glass and I may start producing one of them (a modern day optimized Clevenger apparatus).

Some gins are getting really successful. I'm suspecting the cost to accurately standardize botanical charges has to becoming viable for many. What are the biggest micros performing?

I would love to start some discussion here, but if anyone want to discuss very specific things privately, feel free to DM me.

[bostonapothecary]

I don't know where people are with exploring chromatography based analysis, but I just wrote a fun post about birectifier assisted chromatography.

In the fall, I attended a conference in Jamaica where pretty much all the distilleries used chromatography (and ran 3 shifts around the clock!), but all wished they did more with organoleptic analysis and possibly olfactometry. A lot of the compounds producers are missing are derived from carotene and very hard to look at. These turn out to be the highest value components in a spirit, be it rum or bourbon. The birectifier becomes the cheapest way to evaluate them and the smartest way to contextualize them and tie them to decision making during production.

This post was in response to three different university labs requesting birectifier samples. They wanted to look at what was in fraction 5 and possibly name the compounds that Arroyo called "rum oil". They keep insisting on 100 ml samples, but I had to explain that traditional birectifier samples are already concentrated 10x! If I sent one to further concentrate for chromatography, it would already be a better than average starting point. We'd also have more context than usual because we know the band of volatility we are looking at and we can repeat the birectifier work on the cheap.

I'm making slow progress, but the birectifier is attracting some of the world's great labs and hopefully will be a part of research papers that will be especially useful to craft distillers.

[Roger]

love your enthusiasm, perfectionist attitude and approach, but I have to ask, what's the real goal ?  Beyond that, why do you think any small distiller even cares ?

the products we make either taste good, or they don't. For clear spirits they are as clear as ones equipment can make them, and for aged spirits the flavor profiles at distillation will change so dramatically during maturation that they make the initial information gained from your exhaustive process, vitually meaningless. 

The fact that on day one, a specific batch of bourbon had 1/10,000 of congener ax1, vs 3/10,000 is almost nothing but noise, considering that one will not even know what the product will actually taste like for 5 years. Even then the blender will just attempt to hit a representative sample by blending a certain amount of different products with their nose.

it seems like your incredible attention to detail would be better (and more profitably) served in something like the medical field, vs determining minutia about something so  banal as alcohol. In fact one could assume by the lack of responses to your OP, that this field of endeavor may be very limited. 

prost/Roger 

[bostonapothecary]

Hi Roger,

There clearly isn't much interest here, but interest/sales are coming from the Caribbean and the largest new players. There is also interest from university programs and a few PhD projects. There definitely isn't much of a profit motive.

Some of these congeners have extremely low thresholds of perception, so very small quantities are surprisingly very meaningful. Best bets are emerging on how to maximize them just through practical operation and nothing exotic. It is kind of like trying to cook the same dish as a chef with modest ingredients. You make something edible while they take the same ingredients, seem to understand a few more variables, and manage to create something far more appealing with no more effort than you. Ingenuity.

During maturation, we know what is changing. During distillation we know what is going where and what is being formed. Garbage in, garbage out. Fermentation is the climax of production. The U.S. and other countries conducted decades of public research for entrepreneurs to build sound private enterprises upon. It blows my mind that it is so easily dismissed. The birectifier project aims to give one affordable and practical tool to use to compete against deep pocketed multi-nationals with million dollar labs. To have no tools but a pH pen is kind of crazy especially when people are investing millions.

You can lead a horse to water, but you can't make it drink. Hopefully it should at least be comforting to know tools and ideas are readily available. Good luck.

[Roger]

 

My commentary is not meant to be negative, it is just one distillers look at your offerings to if nothing more, allow you some insight into your future endeavors. 

prost/Roger 

 

 

[Silk City Distillers]

On 7/18/2018 at 8:10 PM, bostonapothecary said:

Lots of people are buying big ticket u-tube densitometers before they buy other tools like automatic titrators, but is that a good idea? One of my projects is trying to add pycnometry to my analysis tool set as a stepping stone before a u-tube densitometer.

Nobody really considers the u-tube densitometer an analytical tool, it's a productivity tool.  It does not tell you anything you don't already know, or can't determine with a glass hydrometer and thermometer (more accurately), it just does it faster.  The value of the tool, and why so many people invest in them, is time savings and ease-of-use.  Sure, the larger benchtop units give you a very accurate and reliable measurement, but even in this case, it's still not new information.  While the expensive benchtop units are more about assurance (insurance?), the handhelds are about time, and time is always at a premium in a craft distillery.  Paar probably sells hundreds of handheld units to every benchtop unit.

[Southernhighlander]

boston apothecary,

 

I have a question, but not about beverage ethanol distilling.    What instruments would a person use to check a sample of denatured ethanol for percentages of heptane and ethanol?  I know that I can spend thousands on equipment to do this or send it to a lab, but is there any way that I can do it inexpensively in house?

 

thank you.

[bostonapothecary]

On 1/6/2019 at 7:31 AM, Silk City Distillers said:

Nobody really considers the u-tube densitometer an analytical tool, it's a productivity tool.  It does not tell you anything you don't already know, or can't determine with a glass hydrometer and thermometer (more accurately), it just does it faster.  The value of the tool, and why so many people invest in them, is time savings and ease-of-use.  Sure, the larger benchtop units give you a very accurate and reliable measurement, but even in this case, it's still not new information.  While the expensive benchtop units are more about assurance (insurance?), the handhelds are about time, and time is always at a premium in a craft distillery.  Paar probably sells hundreds of handheld units to every benchtop unit.

Productivity has been a hard lesson to learn. Accurately measuring ABV is such a time suck that the Anton Paar tools keep seeming more attractive. It's been slow progress coming up with an alternative. I've got my glass guy trying to make a jumbo Lang-Levy pipette to replace the really poor quality pycnometers on the market, but its been back to the drawing board a few times.

[bostonapothecary]

16 hours ago, Southernhighlander said:

boston apothecary,

 

I have a question, but not about beverage ethanol distilling.    What instruments would a person use to check a sample of denatured ethanol for percentages of heptane and ethanol?  I know that I can spend thousands on equipment to do this or send it to a lab, but is there any way that I can do it inexpensively in house?

 

thank you.

This is way over my head. I had to look up heptane. I don't have much formal science background besides reading obsessively and spending a ton of time playing with things. My interest in analysis has been learning the minimum to bring larger dreams to life. The big lesson from the Judgement of Paris in the wine world was that fine wine was born in the lab. What all the wine makers that won had in common (Mike Grgich, Warren Winierski, et. al.) was that they were routine lab work guys from larger operations like Mondavi. To execute their vision of fine wine, they knew it required the lab. They weren't exactly scientists and were only sitting in on night classes at UC Davis. The birectifier stuff tries to parallel that story. When it comes to something like a denaturant, it is way over my head, but I do think I know who to ask.

[Silk City Distillers]

I thought the cannabis extractors didn't care about heptane in their denatured alcohol, since in the rotovap or vac still it distills with the ethanol and doesn't remain in the product.  It forms a difficult azeotrope, that's why it's used for denatured alcohol.

Seems like heptane denatured ethanol is becoming the defacto standard for tax-free ethanol in that market.

https://ultrapure-usa.com/marijuana-solvent-extraction-botanasolv/

https://710spirits.com/tell-me-more/

 

[bostonapothecary]

Oh wow, I would have thought heptane was from the fuel ethanol world and not the cannabis world. Doesn't it have properties that can help dry ethanol?

[bostonapothecary]

I wrote a post on what to consider when making cuts. A lot of the ideas are based on using the birectifier as an analysis tool to ensure you are distilling at the peak potential of your ferment. This was brought on by a new distiller's questions and by a unique case study where we looked at a tails fraction and found a startling quantity of high value congeners that were just not making it into the hearts. Not many realize that what is high value is less volatile than fusel oil. Something I'm consistently seeing in new American spirits is that they are too light on ethyl acetate. Simple analysis, especially of role models, may help hone in on ideal amounts.

[Southernhighlander]

7 hours ago, Silk City Distillers said:

I thought the cannabis extractors didn't care about heptane in their denatured alcohol, since in the rotovap or vac still it distills with the ethanol and doesn't remain in the product.  It forms a difficult azeotrope, that's why it's used for denatured alcohol.

Seems like heptane denatured ethanol is becoming the defacto standard for tax-free ethanol in that market.

https://ultrapure-usa.com/marijuana-solvent-extraction-botanasolv/

https://710spirits.com/tell-me-more/

 

I actually sell equipment to businesses that are separating oils from plant materials, such as nutraceuticals companies and companies extracting oils from hemp.  Just like anything the devils in the details.  As you can probably imagine many of the people that do this do not want poison as part of their process, even if they can remove it all.  Also there is another issue with it.  If distillation for reclamation and oil concentration for CBD occurs at or above 110 F then some of the CBD will be cooked off.  Ethanol and Heptane form an azeotrope with a boiling point under one atmosphere of 208 F while ethanol has a boiling point of 173.1 F under 1 atmosphere.  So if I pull -29 inHg gauge and I am using oil laden ethanol that has not been denatured, then my average boiling point is around 80 F or slightly less, however if i am using ethanol denatured with heptane my boiling point is significantly higher.  When the solvent is mostly cooked off the temp gets higher still.  Also under vacuum the azeotrope that is ethanol and heptane is general broken and heptane is the product that is in the oil in a few parts per  once vacuum distillation is complete.  Can it be done with denatured,yes it can but non denatured ethanol is a better solvent to work with.  That being said why would someone want to even use denatured? of course the answer to that is price.  If they have been doing cbd from hemp and THC from cannabis they cannot get tax credits for their ethanol purchases.  Now that hemp is legal under federal law that may change for cbd, however until cannabis is legalized under federal law that will not change for THC extractors.  Also all of the solvent is not removed in the vacuum still or rotary evaporator in these processes. Usually once a ratio of 3 part oil to 1 part ethanol is reached the oil is removed from the vacuum still for further processing in a vacuum oven. It is done this way because of the viscosity and stickiness of the pure oil.  Also the time factor plays a part in this.  

All of that being said I will not be producing ethanol for extraction purposes.  i will be buying denatured and strait ethanol and reselling it for extraction purposes.  I will be buying in large volume to maximize my profit.  I was asking about the heptane because i want to check the denatured that i purchase and make sure the percentages are what the manufacturer says they are.  

Also I sellequipment for extracting oil from plant materials.  I do not sell any equipment specifically for cannabis as that would be illegal under federal law.

[bostonapothecary]

I know temperature is an unreliable thing to measure, but could you reflux it and try to measure the temp of the azeotrope to make sure it is in spec? Or are you concerned with measuring what is left behind in the oil?

I thought the tax thing would not be that big a deal because you'd be able to reuse the solvent over and over?

[Silk City Distillers]

Yeah, I'd also assume you could infer the concentration by measuring the temperature at boiling point at a specific pressure.  It might be easier to do this under vacuum.  Measure the boiling point of a laboratory tested sample - and compare subsequent samples to this boiling point.  The BP is not likely to be a simple linear function though, so you wouldn't necessarily be able to easily determine the concentration, unless you had a table to compare against.

That said, you could just get some 200 proof ethanol, some heptane, mix them in known ratios, and test the boiling point of each at a specific pressure.  Then, plot out a graph of the boiling point vs concentration.

However, this is pretty crude, assumes only a binary azeotrope, adding water to the mixture complicates this immensely.  So old solvent that has absorbed water, will likely read as having a higher percentage of heptane than it actually does.

 

[bostonapothecary]

22 minutes ago, Silk City Distillers said:

Yeah, I'd also assume you could infer the concentration by measuring the temperature at boiling point at a specific pressure.  It might be easier to do this under vacuum.  Measure the boiling point of a laboratory tested sample - and compare subsequent samples to this boiling point.  The BP is not likely to be a simple linear function though, so you wouldn't necessarily be able to easily determine the concentration, unless you had a table to compare against.

That said, you could just get some 200 proof ethanol, some heptane, mix them in known ratios, and test the boiling point of each at a specific pressure.  Then, plot out a graph of the boiling point vs concentration.

However, this is pretty crude, assumes only a binary azeotrope, adding water to the mixture complicates this immensely.  So old solvent that has absorbed water, will likely read as having a higher percentage of heptane than it actually does.

 

I think the other limiter is that temperature is hard to know exactly. It may give you a pretty big margin of error. You're making me feel a lot better about sticking with beverage distilling. Its a lot easier to wrap one's head around.

[Southernhighlander]

4 hours ago, bostonapothecary said:

I know temperature is an unreliable thing to measure, but could you reflux it and try to measure the temp of the azeotrope to make sure it is in spec? Or are you concerned with measuring what is left behind in the oil?

I thought the tax thing would not be that big a deal because you'd be able to reuse the solvent over and over?

After consideration I think that I'm just going to send some samples off to a lab for testing and then consider that companies product good That's what I have done with chinese copper and stainless from time to time.  It's not that I'm not trusting, i just like to verify.  

Because of certain aspects of the process not all of the ethanol can be reclaimed.  Losses can be as high as 15% per run.  I have shaved that down to less than 1/2 of that with my process.  typically most of the loss is from the residual ethanol left in the plant material after extraction.  This not only amounts to a significant loss it is dangerous because that plant material  is flammable.  My fix is simple and common sense.  My wash/extraction vessels have a connection for a small short path column and extension and a knock out for vacuum connection as well as a cold trap and small receiving vessel. Basically the wash vessel becomes a still, distilling off and reclaiming residual ethanol.  i don't know of anyone else in that industry who has done that.  Also some ethanol is left behind in the lipids when they are filtered out at  - 40 C. 

Most competitors in that industry are selling large scale rotary evaporators and larger falling film evaporators.  They come at everything from a laboratory direction.  All of that glassware is incredibly expensive especially when you are talking about 48" diameter rotary evaporators that must handle -29inHg gauge.  My equipment is stainless and once you get above 50 gallon capacity my equipment can cost 1/10 of the price of some lab glass systems.  At this point in the hemp CBD business industrial size process systems are needed because now you suddenly have row crop farmers involved that can grow 3,000 acres of hemp. In my East Tennessee Hillbilly opinion, glassware extraction systems are about to become obsolete.  It's time to put some size into it. Those that don't may not survive into the next decade.  There are a couple of other companies in the hemp industry selling stainless equipment but all except for me and one other are doing things pretty small. The others systems onlygo large enough to process the oil laden ethanol from a few hundred lbs of plant material per run

  I have systems out there in place now that will process the oil laden ethanol from thousands of lbs of plant material per day.

If you think this part is complicated.  Doing isolates is like alchemy to most people in this industry. Cracking columns (fractining columns with draw offs at every plate set up to fraction out all of the different chemicals by boiling point)are not being used.  they are using lab equipment to do  1 fraction at a time unless they are using wiped film and that will only do 2.  I was lucky enough to build some small r nd d cracking columns for some chemists who where working with crude oil in TX a few years ago.  I built them a 26 plate with draw offs at every plate that was fractoining out 25 different chemicals.  I'm really glad i had the opportunity to do that.  It was actually a real challenge because of the temps involved.

[Southernhighlander]

4 hours ago, Silk City Distillers said:

Yeah, I'd also assume you could infer the concentration by measuring the temperature at boiling point at a specific pressure.  It might be easier to do this under vacuum.  Measure the boiling point of a laboratory tested sample - and compare subsequent samples to this boiling point.  The BP is not likely to be a simple linear function though, so you wouldn't necessarily be able to easily determine the concentration, unless you had a table to compare against.

That said, you could just get some 200 proof ethanol, some heptane, mix them in known ratios, and test the boiling point of each at a specific pressure.  Then, plot out a graph of the boiling point vs concentration.

However, this is pretty crude, assumes only a binary azeotrope, adding water to the mixture complicates this immensely.  So old solvent that has absorbed water, will likely read as having a higher percentage of heptane than it actually does.

 

Great points and that would be doable, but my idea was if I could get some simple instruments I would test here otherwise I guess it is off to the lab.  I will probably not test very often anyway, because in all likelihood things are what the manufacturers say.  I've just learned to be weary over the years concerning anything I am going to by and sell to others. 

Also to be truthful i do a lot of equipment testing to collect data and improve the equipment and the process.  i extract oil from hops which is a cousin to hemp.  I am in the dark about whether i am breaking the azeotrope and whether the ethanol is fractioning out completely under vacuum once I only have 5% left in the pot, at what boiling point is the heptane being fractionated out completely and on and on and on?  

[bostonapothecary]

Recently, I used the birectifier to look at the tails fraction of a full bodied rum. The results were very cool and quite insightful. Fusel oil was shown blocking a significant portion of high value congeners from entering the spirit. If fusel oil could be reduced, more HVC's could be captured and spirit quality improved. The birectifier made examining and making sense of it fairly easy. We generated great actionable insights with the minimum of hard science.

[bostonapothecary]

Recently, I started exploring titration for acids and ester determinations and wrote a primer. Is anyone here currently using titration in their analysis work that is willing to offer some tips?

I'd love an automatic titrator, but working affordably so the work can be duplicated by others is important.

My goals are to accurately measure titratable esters in a spirit and then subtract the ethyl acetate isolated in the first three birectifier fractions to create a ratio of low value to high value esters. Arroyo worked with a similar ratio in Studies on Rum. I'd also like to be able to create numbers that can bring more of the historic data tables to life. Tracking the development of ethyl acetate is important to understanding maturation.

Titratable acidity is key to working with ferments that feature large buffers and significant noble volatile acid production.

I'll hopefully add these basic titration results to my birectifier role model case studies.

Any tips, tools, suppliers, or calculators you like?