technologist
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Nitration or Chlorination of Alcohols
Looking for process conditions & catalyst for Nitration OR Chlorination of aliphatic alcohol mixture of C2, C3 & C4.
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chemrox
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You're asking a lot of basic organic chemistry questions. While it may be good for me (and others) to think about them, you should be looking these
up yourself. A lot of good books have been posted here by generous members. Please consult them.
"When you let the dumbasses vote you end up with populism followed by autocracy and getting back is a bitch." Plato (sort of)
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Sauron
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When you say "process conditions" that sounds like an industrial scale. Catalyst is in line with that.
On a bench scale there are a multitude of ways to replace aliphatic -OH with -Cl
See Vogel for the classical methods, also:
TCT (cyanuric chloride) and DMF - fast and quantitative
to mention only two.
Regarding nitration, those nitro esters are highly explosive.
If you are talking about making nitroalkanes, totally different story. That IS an industrial process, and DOES involve catalysis, I suggest you read
about it in Ullmann or Kirk-Othmer.
Sic gorgeamus a los subjectatus nunc.
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technologist
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I understand that these are basic questions. But I am a chemical engineer involved in technology & process improvement at commercial scales.
Therefore, my problem is that I dont need only textbook theory. That's why I came to this forum bcoz U people have great hands on experience on these
common things based on your lab experiments which are more realistic for me to build upon.
In the current case, I was looking for some value addition to Fusel Oil which is a mix of C2, C3, C4 & C5 (n & iso) alcohols.
Its easy to mention conventional things which are practically & sometimes economically are not viable and also as a manufacturer U dont have great
advantage in following what others are doing.
So I found that fractional / Azeotropic Distillation / Esterification etc etc....are not commercially viable. Therefore, thought to convert them to
chlorides which are volatile for C2 & C3 and to some extent C4 also. This eliminates my problem of separation of lower molecules from the mix and
I am left with some C4 & C5 majority.
This can then be converted back to alcohol by alkali or may be re-transformed.....Saving lot of cost even after involving Cl2 & Alkali.
Or as second option
I used Sieves to dry out this Fusel Oil to less than 0.5% Moisture from 5% moisture. It was done successfully in the lab but no Complete package
supplier (of Molecular Sieve Dryer System) is ready to quote for this entire turnkey plant.
Any Input????
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not_important
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Hmmm ...
| Quote: | | A commercial hydrophilic membrane, PERVAP-1001, was applied for the dehydration of natural fusel oils by membrane pervaporation. The fusel oils
dehydrated to di erent levels (1.5 mass %, 5 mass %, and 9 mass % of water) by pervaporation as well as a raw fusel oil were subjected to batch
fractional distillation. During pervaporation, a high selectivity of the investigated membrane toward water was found. The results of distillation
showed that the fractionation of fusel oil containing less than 5 mass % of water yielded a much better separation of lower alcohols.
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Attachment: Separation of Fusel Oils.pdf (165kB)
This file has been downloaded 626 times
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Sauron
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Fusel oil is a term generally used to describe C4-C5 isomeric mixtures of congeners from fermentation of ethanol (C2).
The best way to reduce these is a fixed bed of granular activated charcoal (GAC) with the alcohol (ethanol) diluted to 50%. This does not work with
either the 95% azeotrope or anhydrous ethanol because the strong ethanol will leach the higher alcohols out of the GAC as fast as the GAC will adsorb
them.
This is the method used to purify vodka.
Fusel oils are only present in small amounts. Any method to convert the C4-C5 alcohols to chlorides will also convert the ethanol to highly volarile
ethyl chloride. This is obviously unacceptable for potable ethanol. If you are manufacturing fuel ethanol I fail to see why the butyl and amyl
isomers need to be removed.
Sic gorgeamus a los subjectatus nunc.
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not_important
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| Quote: | Fusel oil is a by-product of distilleries, its average composition
is 10% ethanol, 13% n-propanol, 15% i-butanol, 51% iamyl-
alcohol, 11% miscellaneous alcohols and water. Nowadays
fusel oil is usually burned to complete the energy demand
of the distilleries.
...
Biolubricant was prepared in integrated system by an esterification reaction of fusel oil and oleic acid, where immobilised Novozym 435 lipase enzyme
was used as a biocatalyst. Firstly shaken flasks experiments were carried out, and the effects of water content, temperature, substrate concentration
and the molar ratio of oleic acid and alcohols on the ester yield were investigated in solvent-free system. To eliminate the negative effect of the
water produced in the reaction, integrated system was constructed, and pervaporation was used for water removal. The method was suitable to achieve
99.8% conversion under optimal conditions. |
In the USA there appears to be a large demand for biolubricants these days.
Attachment: biolubricant.pdf (127kB)
This file has been downloaded 1000 times
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technologist
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Dear Sauron
Actually I think I have not mentioned my post properly.
We are obtaining ~10 KL/Day of Fusel Oil from our distilleries after producing Ethanol. SO this Fusel Oil is already separated from ethanol
purification steps.
Now what are the commercial feasible value additions possible?
That is my concern. Related to pervaporation can U (not_important!........ in fact U r important one) tell me the supplier of the same.
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technologist
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In fact ours Fusel Oil is
Moisture - 10%
C2 - 8%
C3 - 1%
C4 - 9%
C5 - 72%.
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Sauron
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In that case, chlorination will give you a good way to seperate your small %age of C2 and C3 by fractionation. The C3 may cobtain both the n-propyl
and isopropyl isomers.
The C4 and C5 fractions will be more complex and perhaps less amenable to fractionation.
From 10 KL a dya you should have 1800 L of C2/C3 and the balance C4/C5 isomers, is it worthwhile investing the cost of chlorinating, fractionating and
then hydrolyzing these?
All of the products are cheap chemical commodities.
Lowest cost chlorinating agent will be hydrochloric acid or Nacl/sulfuric acid.
Surely you have a breakdown of the C3, C4 and C5 isomers present? In theory there could be as many as ten or so C4 and C5 isomers.
Sic gorgeamus a los subjectatus nunc.
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not_important
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| Quote: | Originally posted by technologist
That is my concern. Related to pervaporation can U (not_important!........ in fact U r important one) tell me the supplier of the same.
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I'd check on the sources given by the two articles, at least one of which was apparently for a complete apparatus.
The bio-lubricant concept might be a decent product, although both research and market development would likely be needed.
Another thing to look into is reactive distillation - just do a Web search. This combines the reaction step, say esterfication, with fractional
distillation. It can frequently tolerated water, which will be a product as well, in the feedstock. If the market prices for say the acetates is high
enough this could be a economically practical route to them directly using the raw fusel oil you currently produce.
And you could send me a small barrel of crude fusel oil ;-)
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zeppelin69
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OT: I am sorry to break up the thread and I do not mean to lead it astray, but Technologist, I must know. How can you bring yourself, after writing
such a good post with proper spelling and grammar, to use childish abbreviations such as U and U r? Those sorts of things belong in text messages
between 12 year old girls, not a professional chemist inquiry.
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smuv
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I think he is purposely trying to make his writing style look different as to avoid recognition. I can see no other reason, as I have noticed the
same.
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Sandmeyer
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A while ago, there used to be someone supposedly from India who used to abuse and exploit the forum in manner similar to technologist. Maybe it's the
same wine in new bottle.
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technologist
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Dear Sauron
Ur concern is right but My reply is as below.
1. On moisture free basis the components will be
C2+C3+C4 = 20%
C5 = 80%
So I will be planning to recover C2 from vapor phase which is ~10%.
And C4 from liquid phase which is also ~10%.
2. We dont have nay isomer of C3 (C2 anyway doesnt have one).
3. C4 is also only normal - NO Isomer.
4. C5 is having both Iso Amyl & n-Amyl which is most valued for me for downstream conversion.
With this philosophy if I can simplify the process then the cost of separation (Energy cost) saved is more than value addition in terms of products.
This is bcoz my End product is not chlorinated derivative......There will be further value addition after separation. U can imagine that the price
goes as high as 5 times compared to the price of Fusel oil as it is.
I was looking for some suggestion based on experience of GREAT people here for chlorination conditions....I am planning to carry out these trials
myself based on my literature research.......but to have some starting guidelines and possibilities of this process again based on ACTUAL EXPERIENCE
IF ANY.........it was posted here.
NOT TO CARRY OUT SEARCH OR RESEARCH FOR ME.
I am not going to answer on the post after I made to chemrox (See the sentiments, no response from chemrox while others are worried.....No offense
from my side compared to the language used by many........My SMS language style........just for saving my precious time nothing else.........anyway
they r free to let out their frustration).
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technologist
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Dear Important.......
I extensively searched on reactive distillation also but the azeotropes complexes in this mixture are so typical that first you need.....
1. More than 40 stages which means very tall column.
2. Very high energy consumption....
3. More capital intensive.......
Prices are good but when U compare market competition for acetates it is disadvantageous compared to those r manufacturing thru direct routes or pure
chemicals.
Therefore, I thought about exploiting other reactions.........
Reg Bio-Lubricants I need more info as I've not explored in this area....How it is Bio-Lubricant if derived from Fusel Oil.............
My other search led me to Nitration of Fusel oil & separation but I found chlorination better than nitration as resultant chlorides r more
volatile & easily separable.
 Why a samll barrel, come to my plant and we will give you entire storage of
FO........Ha...Ha...Ha
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Sauron
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I suppose the amyl acetates and perhaps other esters could be exploited for flavor & fragrance use if they are rigorously purified to FDA and
related standards.
Such a low %age C3 helps simplify, as does having only n-butanol.
So you will recover about 1 KL a day of ethanol and same of butanol, and the balance are two C5s (normal and iso). 8 KL a day.
Cool.
Do you have access to Ullmann and/or Kirk-Othmer? If not let me know and I will extract the alkyl chloride sections and post them here for you.
Sic gorgeamus a los subjectatus nunc.
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not_important
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| Quote: | Originally posted by technologist
...
Reg Bio-Lubricants I need more info as I've not explored in this area....How it is Bio-Lubricant if derived from Fusel Oil.............
...
Why a samll barrel, come to my plant and we will give you entire storage of
FO........Ha...Ha...Ha |
Bio-lube because it quickly degrades via biological processes if spilled or released into open environment; and it's non-petroleum derived. This
gives it additional market value in some regions, how much I don't know. Given as it is a pretty straight forward esterfication, of a sort that does
work well with reactive distillation 8-), it might be relatively low cost to produce; again there's no need to dry the fusel oil first and the
vegetable oil/fatty acid feed need not be dry either - even filtered waste fats would do.
A barrel of fusel oil is plenty for me, benchtop lab and all that :-;
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JohnWW
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| Quote: | Originally posted by technologist(cut)
1. On moisture free basis the components will be
C2+C3+C4 = 20%
C5 = 80%
So I will be planning to recover C2 from vapor phase which is ~10%.
And C4 from liquid phase which is also ~10%.
2. We dont have nay isomer of C3 (C2 anyway doesnt have one).
3. C4 is also only normal - NO Isomer.
4. C5 is having both Iso Amyl & n-Amyl which is most valued for me for downstream conversion.
With this philosophy if I can simplify the process then the cost of separation (Energy cost) saved is more than value addition in terms of products.
This is bcoz my End product is not chlorinated derivative......There will be further value addition after separation. U can imagine that the price
goes as high as 5 times compared to the price of Fusel oil as it is. |
I presume you are talking about isomeric higher alcohols. There ARE, in fact, two isomeric C3 simple alcohols - n-propanol (or propan-1-ol) and
isopriopanol (or propan-2-ol), used industrially as solvents. There are bound to be at least traces of both in fusel oil. Similarly, there are FOUR
isomeric butanols - n-butanol or 1-butanol, isobutanol or 2-butanol, tert-butanol or 2-methyl-propan-2-ol, and 2-methyl-propan-1-ol. The two latter
have branched carbon chains, and again it is unrealistic to suppose that of these, only n-butanol is in fusel oil. These exclude cyclopropanol,
methylcyclopropanol, cyclobutanol, the two isomeric bicyclobutanols, and enols, which have different formulae, containing less hydrogen than the
non-cyclic saturated alcohols.
As for isomeric non-cyclic saturated pentanols or amyl alcohols, which as the acetate esters are used as industrial solvents and as a banana flavor,
there are, again, other isomers besides n-amyl and isoamyl. There are three straight-chain isomers, and five branched isomers.
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Sauron
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I think technologist knows that two isomers of propanol exist. What he is saying is that total C3-ols are 1% of the fusel oil they produce, and he
claims that the 1% (100 L a day out of 10 KL/day FO) is exclusively n-propanol.
Perhaps the 2-propanol congener produced in fermentation was all oxidized to acetone. I don't know. I realize this is peculiar, but it is his
postulate, so there is little point in arguing that there &*ought* to be some 2-propanol around.
As you can see getting any details out of this fellow is like pulling teeth.
Sic gorgeamus a los subjectatus nunc.
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not_important
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I don't see the purpose of the iteration of possible isomers. Fusel oil is a biological product with a relatively stanard list of components, although
the exact amounts of each varies depending on what was fermented, the mix of yeasts, and the distillation process. For example:
54.5% amyl alcohol, 17.8% 2-methylbutanol, 11.2% isobutanol and 9.6% propanol
http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/a...
While the fermentation may produce i-Pr it might be in small enough amounts to be ignored, as Sauron suggested it could appears as acetone which would
appear the the foreshots along with any methanol. But even as the alcohol the azeotrope with water boils only 2 degrees higher than the ethanol-water
one, so it would distill out with the ethanol.
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franklyn
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| Quote: | Originally posted by Sauron
If you are manufacturing fuel ethanol I fail to see why the butyl and amyl isomers need to be removed. |
| Quote: | Originally posted by technologist
Dear Sauron
We are obtaining ~10 KL/Day of Fusel Oil from our distilleries after producing Ethanol.
SO this Fusel Oil is already separated from ethanol purification steps.
Now what are the commercial feasible value additions possible? |
Actually Sauron has a point you may be overlooking
Entering < Fractionation "Fusel oil" > and < "Fusel oil" antiKnock > into Google yielded
these tidbits
http://www.environment.gov.au/atmosphere/fuelquality/publica...
" The C3-C5 alcohols in fusel oil should actually enhance the quality of the ethanol
blend," / "A paper produced by Istanbul Technical University in Turkey in April 1996
shows fusel oil as highly effective in reducing the phase separation temperatures and
increasing the water tolerances of the azeotropic ethanol-unleaded gasoline blends.
F.Karaosmanoglu, A. Isigigiur, H.Ayse Aksoy: “ Effects of a New Blending Agent
on Ethanol-Gasoline Fuels ” Energy & Fuels Vol.10, num.3, 1996.
And these apparently also researched Fusel anti-knock properties
http://www.springerlink.com/content/74h357jxv2k52224
http://www.springerlink.com/content/n062583up0t67778
It seems then that your " I don't know what to do with this " material could be
marketed as is as an octane boosting gasoline additive.
.
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