The Purification Feasibility of

Glycerin Produced During

Biodiesel ProductionBiodiesel Production

S. Soulayman, F. Mustafa, and A. Hadbah

Higher Institute for Applied Sciences and technology, Damascus, P.O. Box 31983, Syria,

ssoulayman@hiast.edu.symail: -E

10/11/2011١ ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي

Contents• INTRODUCTION

• Typical composition of crude glycerin from biodiesel production

• Crude Glycerol Refining

• Problems regarding the decision

• Glycerol Applications• Glycerol Applications

• The chemistry of glycerol

• First proposal

• Second proposal: enzymatic trans-esterificationprocess

• Acknowledgments

10/11/2011٢ ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي

What is Glycerin?• Glycerin (Glycerol) is a clear, odorless, viscous liquid with a

naturally sweet taste. It is derived from both natural and

petrochemical feedstocks. Glycerin occurs in combined form

(triglycerides) in animal fats and vegetable oils and is

obtained from these fats and oils during transesterification,

such as in biodiesel production.

Glycerin currently has over 1500 known uses in many • Glycerin currently has over 1500 known uses in many

different industries ranging from foods, pharmaceuticals, and

cosmetics (USP grade glycerin) to paints, coatings and other

industrial types of applications (technical grade glycerin). It

continues to be one of the most versatile and valuable

byproducts created during biodiesel production.

٣ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

٤ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

٥ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

٦ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

Properties Crude Glycerin Technical Glycerin 99.7 -USP Glycerin

Glycerol Content 40 - 88% 98.0 Min 99.70%

Ash 2.0% Max N/A N/A

Moisture Content N/A 2.0% Max 0.3% Max

Chlorides N/A 10 ppm Max 10 ppm Ma

Color N/A 40 Max (Pt - Co) 10 Max. (APHA)

Specific Gravity N/A 1.262 (@25C) 1.2612 Min

Sulfate N/A N/A 20 ppm Max

Assay N/A N/A 99.0 - 101.0% (on dry basis)

Heavy Metals N/A 5 ppm Max 5 ppm Max

Chlorinated Compounds N/A 30 ppm Max 30 ppm Max

٧ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

Chlorinated Compounds N/A 30 ppm Max 30 ppm Max

Residue on Ignition N/A N/A 100 ppm Max

Fatty Acid & Ester N/A 1.00 Max 1.000 Max

Water 12.0% Max 5.0% Max 0.5% Max

pH (10% Solution) 4.0 - 9.0 4.0 - 9.1 N/A

DEG and Related Compounds N/A N/A Pass

Organic Volatile Impurities N/A N/A Pass

Organic Residue 2.0% Max 2.0% Max N/A

Introduction-0- Base Equation

٨ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

100 kg vegetable oil + 15 kg methanol + 2 kg NaOH = 100

kg biodiesel (methyl ester) + 15 kg glycerol (raw) + 2 kg

irresponsive components

Introduction-1- Prospects

٩ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

Property Value Unit Genetically modified origin Possible Glycerol content 77 – 90% wt% A.R. Ash content 3,5 – 7% wt% A.R. Moisture content 0,1 – 13,5% wt% A.R. Lower calorific value 14,9 – 17,5 MJ/kg A.R. Kinematic viscosity 120 mm

2/s

3-monopropylenediol 200 – 13.500 ppm Methanol 0,01 – 3,0% wt% Matter organic non glycerol 1,6 – 7,5% wt%

Typical composition of crude glycerin from

biodiesel production

١٠ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

Matter organic non glycerol 1,6 – 7,5% wt% pH 4,5 – 7,4 Sulphate 0,01 – 1,04 wt% Phosphate 0,02 – 1,45 wt% Acetate 0,01 – 6,0 wt% Na 0,4 – 20 g/kg K 0,03 – 40 g/kg Ca 0,1 – 65 mg/kg Mg 0,02 – 55 mg/kg Fe 0,1 – 30 mg/kg Mn <0,5 mg/kg

Crude Glycerol RefiningTypically produced glycerol is about 50% glycerol or less in

composition and mainly contains water, salts, un-reacted alcohol, and

unused catalyst (see table).

The unused alkali catalyst is usually neutralized by an acid. In some

cases, hydrochloric or sulphuric acids are added into the glycerol

phase during the re-neutralization step and produce salts such as

sodium chloride or potassium sulphate, the latter can be recovered

for use as a fertilizer. Generally, water and alcohol are removed to for use as a fertilizer. Generally, water and alcohol are removed to

produce 80–88% pure glycerol that can be sold as crude glycerol.

In more sophisticated operations, the glycerol is distilled to 99% or

higher purity and sold in different markets.

After the re-neutralization step, the alcohol in the glycerol phase can

be removed through a vacuum flash process or by other types of

evaporators. Usually, the alcohol vapor is condensed back into liquid

and reused in the process

١١ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

Problems regarding the decisionIt can be concluded that the current problems around glycerin

are (and with increasing severity):

• Refinement of glycerin currently is very expensive and

complex, which disqualifies the product for high-quality use.

• The market is overwhelmed with crude glycerin with a price

window of 0 to +150 Euro/tonne, with a low-quality window of 0 to +150 Euro/tonne, with a low-quality

application in combustion, digestion and a sharply increasing

export to USA and China. 440-580 €/tonne glycerin (99,5%)

• The amount of glycerin production from biodiesel is at 1,9

Mtonnes/yr so high, compared to the current market of 0,9

Mtonnes/yr, that additional high-quality chemical and

pharmaceutical applications need to be identified.

١٢ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

Glycerol ApplicationsAlthough biodiesel is the desired product from the

reactions, the refining of glycerol is also important due

to its numerous applications in different industrial

products such as moisturizers, soaps, cosmetics,

medicines, and other glycerol products. It is one of the

few products that has a good reactivity on sump oil, few products that has a good reactivity on sump oil,

and is extremely effective for washing shearing shed

floor, so it can be used as a heavy duty detergent and

degreaser. It was reported also that glycerol can even

be fermented to produce ethanol, which means more

biofuel can be produced.

١٣ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

١٤ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

The chemistry of glycerol

١٥ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

Glycerol will play a crucial role in future biorefineries

First proposal

In Germany, it is allowed to both use crude

and refined glycerin as a feed (pellet)

ingredient.

• The quality demands for the crude glycerin are

max. 0,5% methanol and min. 80% glycerin

١٦ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

max. 0,5% methanol and min. 80% glycerin

while it is common to use only 2-5% of crude

glycerin in the animal feed mix for poultry and

pigs.

• Proposal: Accept these conditions for crude glycerin.

Second proposal: enzymatic trans-

esterification process -1

١٧ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

Second proposal-2

١٨ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

CONCLUSIONS

Finally, one can mention the following:

• The production of high purity grade of crude glycerol is

economically feasible in local Syrian Conditions.

• The utilization of produced glycerol in different aspects

is urgently important.is urgently important.

• The presented information are really devoted to open

official eye on perspectives of Glycerol Industry.

• Further studies should be developed to produce high

purity glycerol in a pilot scale with meeting the

International standards.

١٩ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

Acknowledgments

• The authors wish to thank Higher Commission

for Scientific Researches for financing a part of

this study. They wish also to thank the

Directory of Higher Institute for Applied Directory of Higher Institute for Applied

Sciences and Technology for accepting the

financing of this project.

٢٠ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011

THANK YOUTHANK YOU

٢١ندوة الكتلة الحيوية الھيئة العليا للبحث العلمي10/11/2011