Green Diesel

What is Green Diesel ?

• Diesel made by hydrotreating

biofeeds to remove oxygen and
break bonds at oxygen linkages
• Works well on triglycerides and high
FFA feeds (vegetable oils and
greases)
• Requires H2
FFA : Fatty Free Acid UOP, 2008
Vegetable Oils Processing Routes

Feed Process Product

Methanol
Biodiesel
Biodiesel Biodiesel
Vegetable Oil Glycerol

H2 Hydro-
processing Green Diesel
Vegetable Oil

UOP 4706F-05
 Biodiesel Balance: The
Problems
13 BBL 99 BBL
100 BBL 8 BBL
Mixed Fatty
Vegetable Oil + Methanol + Glycerol
Acid Esters
(Triglycerides)
(Bio Diesel)

• 8 vol-% of product is low value glycerol

• Requires methanol as a feedstock
• Higher priced vegetable oil feedstocks required
as fatty acids cause operational problems

UOP 4706F-06
 Green Diesel Balance: The
Solution
100 BBL 99 BBL 9 BBL CO2
Vegetable Oil + H2 + Propane +
Green H2O
(Triglycerides) Diesel

 Equivalent volume yield of diesel fuel

 Uses available hydrogen as a feedstock
 No low value liquid by-products
 Can process fatty acids in lower cost
vegetable oils

UOP 4706F-07
Biofeedstock Comparison

Price Carbon Olefins,

Bio Feedstock ($/bbl) Number m-%

WTI/Brent Crude 68 11-22 0

Rapeseed oil 89 16-22 94
Soy oil 75 16-18 84
Palm oil 62 16-18 58
Jatropha oil 44 16-18 77
UOP 4706F-04
 Composition of Oils and Greases
(10-12% Oxygen, Olefins, trace sulfur)

OCO

OCO MW = 700-900

OCO
Triglycerides

HOOC
Fatty Free Acids MW = 200-300
 Green Diesel Reactions
Mild Processing Conditions

• Decarboxylation
Catalyst
Cn COOH nCn + CO2

Catalyst
CO2 + H2 CO + H2O Water Gas Shift

• Hydrodeoxygenation
+3H2
Cn COOH nCn+1 + 2H2O
Catalyst

• Hydroisomerization
H 2
nCn+1 + nCn iCn+1 + iCn
Catalyst
 Cloud Points of N-Paraffins
Carbon Number of Hydrotreated
Cloud Point of Pure n-paraffins Vegetable Oils
Rapesee Palm Soybea
Carbon number Melting Point C
d n
NC13 .3 .1
13 -6.2 NC14 .7 .2
14 5.5
NC15 1.3 13.4 2.7
15 10
NC16 3.0 31.3 6.2
16 18
NC17 25.7 14.6 24.4
17 23
18 28 NC18 60.4 34.3 54.8
19 32 NC19 .7 .1 .9
20 37 NC20 1.6 .3 2.4
21 40 NC21 .7 .9
22 44
NC22 1.6 2.4
Cloud points of N-Paraffins make Hydroisomerization important
Processing Vegetable Oil with the UOP/ENI
Ecofining Process to make Green Diesel
Vegetable
• Upgrade vegetable oil
Make-up
Oil Hydrogen using hydroprocessing
Reactor
Acid Gas
Removal
CO2 • Product is an high
cetane diesel blending
Propane component
& Light
Separator
Ends
• Hydrocarbon product,
Naphtha
or Jet not an oxygenated
Water
compound
Diesel
• Co-production of
Product propane, naphtha, and
high quality jet fuel
2017年10月7日 possible UOP 4706F-10
 Cloud Point vs Iso/Normal
ratio
30

20
Cloud Point, C

10
Canola
0 Soy
0 1 2 3 4 5 6 7 8 Palm
-10

-20

-30
Iso/Normal Ratio
 Green Diesel Process
Performance
Feed
Vegetable Oil, wt-% 100
Hydrogen, wt-% 1.5-3.8
Products
LPG, vol % 8-8.6
Naphtha, vol-% 1-16
Diesel, vol-% 84-99
Cetane Number > 75
Sulfur, ppm <1

Water and CO2 also produced as

deoxygenation products UOP 4706F-12
 Extensive Pilot Plant Testing
to Establish Process Viability

110
Green Diesel, Vol-% Yield

105
100
95
90
85
80
75
70
0 500 1000 1500 2000 2500
HOS

Catalyst Stability Demonstrated

UOP 4706F-11
 Green Diesel Fuel Properties
Petroleum Biodiesel
ULSD (FAME) Green
Diesel
Oxygen Content, % 0 11 0
Specific Gravity 0.84 0.88 0.78
Sulfur content, ppm <10 <1 <1

Heating Value MJ/kg 43 38 44

Cloud Point, °C -5 -5 to +15 -10 to +5

Distillation,
• Superior °C fuel properties
200 to 350 340 to 355 265 to 320
• Compatible with petroleum diesel
Cetane 40
• Compatible with conventional 50-65 engines
diesel 70-90
Stability Good Marginal Good UOP 4706F-13
 Green Diesel
Blending Benefits
• Green Diesel has a high
Diesel Pool Barrels Cetane
cetane and is similar to
Components in Pool Index
GTL and CTL diesel
• Cold flow properties are
controlled by paraffin
isomerization
Kerosene 500 41
• These properties make
Straight Run Diesel 7500 52
Green Diesel a premium
blending component
Hydrotreated LCO 2000 20
• Permits blending low
Green Diesel 2346 74 value LCO into ULSD or
a reduction in cetane
Average Cetane 50
enhancing additives
UOP 4706F-14
 Green Diesel Economics
Sensitivity to Veg Oil Price
$500
$400 $560MT w/Tax Incentive
$560MT
$300
$420MT
$200
NPV, $MM

$100
$0
30.00 40.00 50.00 60.00 70.00 80.00
-$100
-$200
-$300
-$400
-$500
Crude Price, $/bbl

• Palm oil ($420/MT;$1.47/gal): Profitable at crude > $52/bbl

• Soy oil ($560/M ;$1.96/gal): Profitable at crude > $67/bbl
• Soy oil w/ $1/gallon subsidy: Profitable at crude > $38/bbl

Driven by Feedstock Cost

UOP 4706F-15