BTC PTEC Biodiesel Workshop

August 7 8, 2006 Session 2 Chemical Background

Agenda for second session

Biodiesel production Chemistry background Chemical compounds Chemical reactions in the production of biodiesel Material balance

Biodiesel Production
Oil, Fat or Grease Feedstock

Pretreatment
Acid Catalyst Methanol Base Catalyst Water Esterification

Gums / Waxes / Insolubles

Transesterification
Biodiesel Washing Biodiesel Stripping ASTM Quality Biodiesel Methanol and Water Distillation

Glycerine Neutralization Glycerine Stripping Glycerine Distillation USP Grade Glycerine

Chemical background
Biodiesel is made from a reaction of a vegetable oil or animal fat with an alcohol This reaction is called transesterification and produces an ester plus a glycerol We will first look at some chemical structure for compounds of interest in the making of biodiesel Then we will look at the reaction

Chemical compounds
Vegetable oils and animal fats (triacylglycerols)
O CH2 O C R1 O CH O C R2 O CH2 O C R3
R groups are from fatty acids of the form O HO C R

Chemical compounds
Oils and fats are composed of Fatty acids
Saturated fats (no double bonds, C C only)
Good cetane numbers and stability Poor cold weather properties

Unsaturated fats (one or more double bonds, C = C)

Can be oxidized Better cold weather properties

Chemical compounds
Fatty acids
CH3(CH2)14COOH palmitic acid CH3(CH2)16COOH stearic acid CH3(CH2)7-CH=CH-(CH2)7COOH oleic acid CH3(CH2)7-CH=CH-CH2-CH=CH(CH2)4COOH linoleic acid CH3(CH2)7-CH=CH-CH2-CH=CH-CH2CH=CH-CH2-COOH linolenic acid CH3(CH2)7-CH=CH-(CH2)11- COOH erucic acid

Chemical compounds
Things that we will use to make biodiesel are:
Alcohols
CH3OH methanol CH3CH2OH ethanol CH3CH2CH2OH n-propanol OH CH3CHCH3 iso-propanol

Bases
NaOH sodium hydroxide KOH potassium hydroxide NaOCH3 sodium methoxide (sodium methylate, 25% active agent in methanol) (We can determine the amount of catalyst needed by titrating a sample of the vegetable oil with a base)

Chemical compounds
The reaction will produce:
Glycerols
CH2 OH CH OH CH2 OH

Soaps (Na or K) O C - R

Chemical compounds
And the biodiesel products we want are: Esters (examples) O
CH3-C-O-CH3 methyl acetate (methyl ester) O CH2-C-O-CH2CH3 ethyl acetate (ethyl ester)

Other products
Soaps O O

Na O C R

CH2 O CR Mono and diglycerides CH OH O CH OH Free fatty acids HO - C - R

The transesterification reaction

O

CH2 O C R1 O CH O C R2 + 3 CH3OH = 3 CH3OOCRi + O CH2 O C R3

CH2 - OH CH OH CH2 - OH

Triacylglycerol + alcohol = mixture of fatty acid esters (biodiesel) + glycerol

Phases
Biodiesel (upper phase)
Contains esters and some methanol (60:40 split with glycerine phase) Water not soluble in this phase

Glycerine (lower phase)

Also contains contaminants such as soaps
90+% of soap formed

And unreacted chemicals

95+% of catalyst added Alcohol split with biodiesel phase

Fatty acid reactions

Side reactions also occur such as:
Reaction with base to form a soap
R COOH + KOH = R COOK + H2O

A pretreatment reaction we might use is a FA with acid catalyst (H2SO4) and methanol to form an ester
R COOH + CH3OH = R COOCH3 + H2O

Reactions of esters
Other side reactions may be:
Reaction with bases in water or water to form free fatty acids and acylates
O O XOH + RO-C-R = XOR + HO-C-R

Reaction considerations
Need
excess of reactant (100% molar excess of alcohol) a catalyst (acid or base) moderate temperature (60 - 65 deg C, 140 150 deg F) mixing residence time (2 - 4 hours)

Problems may occur from the presence of

Free glycerol (inhibits reaction) moisture (hydrolysis of FA esters at > 0.5%) excess catalyst (soap formation) free fatty acids (soap formation)

Biodiesel from high FFA feedstocks

To remove free fatty acids (FFA) to prevent soaps, we can use
Acid catalyzed esterification to reduce FFA to < 0.5 1% and follow this with Alkali catalyzed transesterification

Or we can just let them form soaps and hope for the best (no emulsion formation and not too much loss of product)

Example mass balance

Reactants
100 pounds of vegetable oil (canola) 23 pounds of methanol (100% excess) 0.4 pounds of sodium hydroxide

Products
100 pounds of ester (assuming 100% yield more commonly it would be 75% for one step and 98% for two steps) 11 pounds of glycerine 12 pounds of methanol (unreacted) 0.4 pounds of sodium hydroxide

Volume balance
Reactants
13 gallons of vegetable oil (canola) 3.5 gallons of methanol (100% excess)

Products
13 gallons of ester 1 gallon of glycerine 1.7 gallons of methanol (unreacted)

Transesterification Material Balance

Catalyst
0.5 to 1.5 lb

Oil Feedstock
100 lb

Methanol
10 lb + excess

Acid

Glycerine

Reaction and Separation FFA

0 to 1 lb

Esters

Water
1 to 100 lb

Acidulation

Waste Water
0 to 100 lb

Washing

Methanol Removal Crude Glycerine

10 lb (pure basis)

Excess Methanol
50 to >99% Biodiesel 95 to 100 lb

Methanol Removal

Other steps in production

Water wash (1 100 pounds) Methanol recovery Glycerine recovery or disposal Water treatment and disposal

Alternative reactant comparison

Alcohol
Costs (methanol often cheapest) Ethanol may be more difficult to recover than methanol, also need more but it is renewable Propanol and higher alcohol derived biodiesels have lower freezing points

Base catalyst
Sodium hydroxide most common in US due to lower cost Potassium hydroxide more effective and is common in Europe, residue can be used as a fertilizer Methoxides used for large scale operations (>5 million gallons/year) do not form water, most active catalyst

Acid catalyst (sulfuric acid), cheap, does not make soaps, very slow reaction

Other chemical issues

Extended storage (>1 year) to result in
Oxidation (rancidity) Polymerization Reactions catalyzed by metals and favored by contact with air, water or sunlight Inhibited by anti-oxidants Microbial attack Polyunsaturated fatty acids most susceptible to oxidation

Safety
Chemicals (Methanol, base, acid)

Disposal of wastes