BIODIESEL GLYCERIN:The consequences and solutions

Sjaak van Loo (Sjaak.vanLoo@procede.nl)

The GTBE® Company

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Procede Group BV (www.procede.nl)

• Activities:Process and Product development based on leading knowledge in process (chemical) engineering

• Markets & clients:• Oil&Gas, Chemical and Food industry• 60% multinationals, 30% SME’s• 10% own technology positions (spin-off’s)

• Resources:• ~ 30 process engineers (all academic, 25% PhD)• Research facilities, laboratories

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General background

• Glycerin is probably one of the first organic molecules known to man (ever since the discovery of soap-making) So its uses are well-developed.

• The peculiarity of glycerin, from any source, is that it is a by-product, so that its production is independent of market demand.

• 10% of oil and fat input for soap, fatty acid and ester manufacture is set free as glycerin.

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Glycerin and Biodiesel (1)

• EU directive EC 2003/30/EG sets targets for renewable transportation fuels:• 2 % of total in 2005• 0,75 % growth per year to 5,75 % in 2010• Two main types: Bio-ethanol & Biodiesel

• Sharply increasing amounts of glycerin produced as by-product from biodiesel production

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Glycerin and Biodiesel (2)

• For every ton of biodiesel 100 kg of glycerin is co-produced, leading to 1 M ton/a glycerin in 2010.

• These quantities are generated over and above the amounts from traditional sources

0

2

4

6

8

10

12

Pro

duct

ion

capa

city

[M

ton/

a]

2005 2006 2007 2008 2009 2010

Year

Biodiesel Capacity in Europe(Joint Research Centre EC, 2004)

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Traditional Glycerin uses (1)

18%16%

14%

11%

11% 10%

8%

6%

2%

2%

2%

12%

drugs/pharmaceuticals18%pers. care 16%

polyether/polyols 14%

food 11%

others 11%

triacetin 10%

alkyd resins 8%

tobacco 6%

detergents 2%

cellophane 2%

explosives 2%

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Traditional Glycerin uses (2)

• Traditional outlets can be expected to show only limited growth (and this at the expense of other polyhydroxy compounds such as glycols and sorbitol)

• Entirely new, large-scale uses for glycerin need to be developed........and fast!

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The Solution: GTBE® (1)

• The most promising new outlet appears to be a new additive for diesel (both fossil- and bio-)

• The target compound is a mixture of the di- and tri- butyl-ethers of glycerin: GTBE®

• It will lead to reduction in emissions of:• Particulates

• NOx

• Hydrocarbons (unburned)

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The Solution: GTBE® (2)

Mono

Di

Tri

Acid kat.

Glycerin

Isobutylene

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The Solution: GTBE® (3)

Working pointNOx

2 g/kWh

ROSI,EGR=High -18%

ROSI,EGR=Low -39%

A100, EGR = 7% -14%

A50,EGR= High -22%

A50,EGR= Low -29%

Average PM reduction

-24%

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The Solution: GTBE® (4)

0

10

20

30

40

50

60

70

80

0 100 200 300 400 500 600 700 800 900

time [min]

wt.

%

0

0,5

1

1,5

2

2,5

TBA

1-GTBE

G

WATER

DIB1

DIB2

1,2,3-GTBE

1,3-GTBE

1,2-GTBE

2-GTBE

45°C

60°C

70°C75°C

90°C

0

20

40

60

80

100

YD

TB

G+

TT

BG [

%]

0

20

40

60

80

100[%]

XG MTBG DTBG TTBG di-i-Bu

45°C

60°C

70°C

75°C

90°C

0

10

20

30

40

50

60

70

0 10 20 30 40 50 60

Water amount (%)

(%)

MTBG

DTBG

TTBG

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The Solution: GTBE® (5)

Sensitivity analysis GTBE/diesel ratio for isobutene and glycerol as reactants; excise included

0.40

0.60

0.80

1.00

1.20

1.40

1.60

1.80

2.00

-100 -50 0 50 100

Variation (%)

GT

BE

/die

sel

rati

o (

-)

iC4 cost price

Diesel cost price

Processing costs

NOx reductionfactorDiether selectivity

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The Solution: GTBE® (6)

• Expertise and IP combined:

• Procede Group BV, NL (Process dev.)• Chemconserve, NL (Market dev.)• Blue Ocean, UK (Fuels)• Rabobank, NL (Green fund)

• Our objective: Develop and implement a production unit for 500.000 t/a GTBE

The GTBE® Company

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The Solution: GTBE® (7)

• Present status:• Its synthesis from glycerin and isobutylene has been

studied up to a first plant set-up and cost price

• Preliminary experimental testing has shown promising results and confirm data from literature

• Industrial feasibility is studied and concluded to be positive

• Process development is ongoing

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The Solution: GTBE® (8)

• Further testing of GTBE in combustion engine laboratories is needed

• Pilot plant research and development of a complete plant design is needed

• Other aspects to be studied:• Environmental and safety aspects (REACh)• Raw materials availability, prices• Process optimization

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Summary

• The EU-directive means by-production of 1 M ton glycerin per annum

• World glycerin use is stable and is not capable to take up this additional amount

• Production of GTBE from glycerin and use it as diesel additive will lower diesel emissions and enable total absorption of the glycerin glut

• International cooperation and funding is needed for further process and market development