Vegyészmérnöki- és

Folyamatmérnöki Intézet
MOL Ásványolaj- és
Széntechnológia Intézeti
Pannon Egyetem
Tanszék
8200 Veszprém,
8200 Veszprém, Egyetem u.Pf. 158.
10. Pf. 158
Tel.: +36 88/624313, +36 88/624413 Fax.: +36 88 624520
Tel.: 88/624313, Fax.: 88/624520

Catalytic Processes of the Hydrocarbon

Industry and Modern Fuels
Bioalcohols and bioethers
Szabina Tomasek, Orsolya Eller-Tóth, Zoltán Eller, András Holló,
László Leveles
Founder of the subject: Prof. Jenő Hancsók

University of Pannonia
MOL Institutional Department of Hydrocarbon and Coal Processing

2021/22 I.
 GASOLINES

Environmental friendly blending

components with high energy content High performance additives
(able to energy transformation in the
operating conditions of engine)

Conventional Alternative

BE-2
OXYGEN CONTAINING COMPOUNDS
ALCOHOLS

• Methanol (methyl alcohol)

• Ethanol (ethyl alcohol)
• Isopropyl alcohol (IPA)
• Buthanol (isobuthanol)
• Tertier buthyl alcohol
• Large carbon number alcohols (cosolvents)

BE-3
MAIN QUALITY PROPERTIES OF ALCOHOL FUEL COMPONENTS

Methyl Isopropyl Tertiary butyl

Properties Ethyl alcohol Butanol Gasoline
alcohol alcohol (IPA) alcohol (TBA)
Density (at 20°C), g/cm3 0.791 0.789 0.786 0.791 0.812 0.720-0.775
Boiling point, °C 65.0 77.8 82.0 82.9 118 20-210
Freezing point, °C -117.3 -97.8 - -25.6 -89 -
Flash point, °C 13 11 11.7 1-5 35 -43-(-)39
Ignition temperature, °C 446 423 - 470 325 460-495
Vapor pressure, at 37.8°C (Reid), kPa 35.5 16.2 13.2 14.2 18.0 50-70
Blending vapor pressure, kPa 413.7 124.1 89.0 82.7 - -
Azeotrope formation with
yes yes - yes yes -
hydrocarbons
Oxygen content, wt % 49.9 34.8 26.6 21.6 21.6 -
Stoichiometric air/fuel mass ratio 6.45 8.97 - 11.3 11.2 14.7
Research octane number (RON) 108 111 112 109 94 95
Motor octane number (MON) 89 92 93 93 81 85
(R+M)/2 98.5 101.5 101.5 101 87.5 90
Cetane number 3 8 - - - 8-14
Energy content, MJ/kg 19.9 27.7 30.3 32.7 35.9 43
Heat of vaporization, kJ/kg 1.150 0.845 0.720 0.598 0.349
Toxicity threshold, mg/kg 1000 200 - 250 790 -
Solubility in water
component in water, v/v % miscible -
water in component, v/v %

BE-4
METHANOL (CH3-OH)

Alternative feedstocks
• Different type synthesis gases (CO + H2)
• Coal
• Natural gas
• Biomass
• Waste (eg. Plastic)

• CO2+H2 (wind plant → electricity → water electrolysis → H2)

Biochemical way

BE-5
METHANOL PRODUCTION FROM SYNTHESIS GAS

Raw materials Methanol synthesis

(coal, natural gas, Synthesis gas Synthesis gas
production purification Methanol
biomass, waste, and separation
hydrocarbons fro (distillation)
mother sources,
etc.)

CO + 2 H2 CH3-OH

High pressure synthesis (100-350 bar)

Low pressure synthesis (<50 bar)

BE-6
ADVANTAGES OF METHANOL AS FUEL COMPONENT

• it can be obtained from well known fossil derived and in part from renewable energy
sources, as well,
• improves the combustion (lower total emission compared even to ethanol),
• lower volatility than of gasoline,
• high research and motor octane number,
• relatively low ozone forming activity,
• it can be transported via pipeline,
• cheaper than ethanol,
• the NOX and particle emission is lower than in the case of conventional engine fuels,
• its flames can be extinguished with water,
• lower combustion temperature than in the case of gasoline (sparing of structural
materials),
• can be applied in fuel cells,
• carbon dioxide emission is reduced when it is produced from biomass,
• several elastomers are suitable for seals (e.g. fluorine silicone rubber, styrene butadiene
rubber, ethylene propylene terpolymer rubber).

BE-7
DISADVANTAGES OF METHANOL AS FUEL COMPONENT

• the energy balance of the production is negative compared to that of gasoline,

• low caloric value (18 MJ/dm3),

• cold start difficulties,

• relatively high methanol emission, very high aldehyde emission,

• toxic,

• good solubility in water,

• high vapour pressure,

• because of its limited solubility, according to the valid European standard (EN 228:2010),
only 3 v/v% methanol can be blended into motor fuels in the absence of a co-solvent.

BE-8
THE BIOETHANOL
(BIO-ETHYL ALCOHOL)

BE-9
REASONS OF BIOETHANOL USE AS FUEL COMPONENT

 Availability

 Octane number improving effect

 Oxygen source (lower emission)

 Renewable energy source

BE-10
PRODUCTION OF BIOETHANOL

BE-11
MAIN FEEDSTOCKS OF BIOETHANOL PRODUCTION

• sugar-plants: beetroot, sugar cane, fodder beet, sugar sorghum;

• crops with high starch content: corn, wheat, barley, potato;

• crops with high inulin content: sweet-potato or sunroot;

• Lignocelluloses: corn-stalk, straw, woody plant parts;

• industrial by-products: molasses, whey, refuse paper, sawdust, etc.

BE-12
PRODUCTION OF BIOETHANOL FROM SUGARS ON DIRECT
AND INDIRECT WAYS

•From simple sugars with fermentation (grape-, malt-, cane-,

beet- etc. sugars),

•From starch with hydrolysis and fermentation (most

spreaded technology in the world),

•From pretreated cellulose with hydrolysis and fermentation

(from agricultural side products, eg. Wood, research phase).

BE-13
BIOETHANOL FROM SIMPLE SUGARS

Simple carbohydrates, sugars.

Crop  mechanical methods(milling, shredding)  sugar syrup

(directly fermentable components: sacharose and glucose) 
anaerob fermentation with yeast  ethanol + CO2 and phosphate
compounds

BE-14
GROSS REACTION OF BIOETHANOL PRODUCTION

CH2OH CH2OH
O
2 CH3 CH2 OH + 2 CO2
H OH
H OH

OH H

C6H12O6
D-fructose ethanol
(sugars)
100 kg 51.1 kg + 48.9 kg

BE-15
BIOETHANOL FROM STARCH (INDIRECT WAY)

starch + water maltose

(C6H10O5)2n + n H2O n C12H22O11 + by-products

glucoamylase
C12H22O11 + H2O 2 C6H12O6
maltose glucose
C12H22O11 + H2O invertase C6H12O6 + C6H12O6
sacharose glucose fructose

BE-16
ETHANOL PRODUCTION WITH FERMENTATION

CO2

optional

Organic feed Shredding, fermentation

pretreating
Water blending,
Utilities pH setting,

aldehydes

Fermented liquid yeast

Ethanol

Alcohol
separation
distillation

Distillation

Fusel oil

Mash

BE-17
PROPERTIES OF THE CORN-BASED ETHANOL
PRODUCTION

 ca. 360-400 l alcohol/t corn

 CO2 formation (fermentation, energetics)

 Side product handling

 High energy demand at the water separation

 High investment and low feedstock costs

BE-18
ETHANOL AS FUEL BLENDING COMPONENT I.
(EN 15376:2015)

Property Unit of Limit

measure
Min. Max.

Ethanol and longer, % 98.7 -

other saturated alcohol
content
C3-C5 saturated % - 2.0
monoalcohols

Methanol content % - 1.0

Water content % - 0.300

BE-19
ETHANOL AS FUEL BLENDING COMPONENT II.
(EN 15376:2015)

Property Unit of Limit

measure Min. Max.
Inorganic chloride mg/kg - 6.0
content
Copper content mg/kg - 0.100
Total acidity (acetic acid) % - 0.007
Appearance Bright and clear
Phosphorous content mg/l - 0.15
Non volatile content mg/100 ml - 10
Sulphur content mg/kg - 10.0
Sulphate content mg/kg - 4.0
Conductivity µS/cm - 2.5

BE-20
E85 FUEL

ca. 85 v/v% bioethanol and ca. 15 v/v% gasoline

BE-21
EFFECTS OF BIOETHANOL ON THE QUALITY OF GASOLINES

• Changing of physical/chemical properties

• Changing of the performance properties

(eg. driveability)

• Effect on emission decreasing

• Compatibility with the materials of engine

BE-22
VAPOR PRESSURE

Ethanol forms negative azeotrope with many gasoline

components (boiling point of azeotrope is lower than
hydrocarbon)  vapor pressure increases (especially in
the lower boiling point range)

• Higher loss from volatility

• Vapor lock forming
• Increasing the vapor pressure standard limit

BE-23
EFFECT OF ETHANOL ON THE DISTILLATION CURVE OF
GASOLINE

120
110 Gasoline
Hőmérséklet, °C °C

Alapbenzin
100
Temperature,

90
80 Alapbenzin
Gasoline
++15%
15%etanol
ethanol
70
60
50
40
30
0 20 40 60 80 100
Átdesztillált mennyiség,
Distillated v/v%
volume, V/V%

BE-24
RESULTS

Fuel pump

„In-line” fuel pump (rotor), ULP/E20 „In-line” fuel pump (rotor), ULP/E20
Before test After test

Corrosion on the axle and on the rotor; contamination of the electrical contacts

BE-25
RESULTS

Polymer components
Tubes: increased diameters, distorsion, inflection loss; initiation of layer and paint
loss

Fuel tube, ULP/E20 Fuel tube, ULP/E20

Before test After test
Risk from the polymer degradation is the particles could cause obstructions in the fuel supply system, in
the filters and in the nozzles.

BE-26
RESULTS

Carburation mixture controller screw, LRP/E20

Before test

Carburation mixture controller screw, LRP/E20

After test
Signs of corrosion all of the brass elements
Corrosion of brass/copper electric connections
BE-27
RESULTS

PVC valves

Pressure controller valve, Pressure controller valve,

LRP/E20 LRP/E20
Before test After test
Components separated from each other (deformation of polymers)

BE-28
RESULTS

Obstruction of injectors caused by the sulphate content of ethanol

BE-29
ADVANTAGES OF ETHANOL AS FUEL COMPONENT I.

• economy with fossil energy sources,

• high octane number (octane number increasing additive),
• contribution to the reduction of the aromatic content of gasolines,
• more perfect combustion (oxygen containing compound),
• higher compression ratio, and thus higher efficiency (38% is reached in some
cases in Brazil),
• increasing driving moment,
• the mixtures have higher volumetric energy content,
• lifetime of engine increases as a result of lower operating temperature,
• numerous environmental advantages: emission of some carbon compounds
(e.g. carbon dioxide by ca. 60-65%, carbon monoxide by ca. 50%), and that of
solid particles decrease,

BE-30
ADVANTAGES OF ETHANOL AS FUEL COMPONENT II.
• biodegradability,
• lower ozone generation ability than that of gasoline (but higher than that
of methanol),
• less toxic than methanol,
• it enables to operate with lean mixture resulting in lower carbon
monoxide and hydrocarbon emission (hydrogen/carbon ratio higher than
in the case of gasoline),
• protection of topsoil and groundwater, improvement of the living
conditions
• social/economical advantages:
•sparing with fossil energy sources,
•increasing of appointability of low trained workers,
•new workplaces in agriculture,
•balanced realization of well-being,
•assisting to the decentralized energy production,
•decreasing of energy dependency.
BE-31
DISADVANTAGES OF ETHANOL AS FUEL COMPONENT

• lower energy content by mass,

• in case of operating with pure ethanol the consumption is higher and the
achievement declines,
• new gasoline blending prescription must be applied because of high blending
vapour pressure and other disadvantageous properties
• high hydrocarbon evaporization emission (e.g. in case of E15G the vapour pressure
of gasoline must be decreased)
• cold start problems in case of pure ethanol (low vapour pressure, high evaporation
heat),
• higher ethane, ethylene and acetaldehyde, but lower formaldehyde emission,
• poor lubrication (damages),
• corrosion (of iron, steel, zinc etc., more corrosion inhibitor is needed),
• absorption of water resulting in phase separation of the gasoline mixture,
• gaskets (elastomers), plastics may be damaged,
• need for tank from special material etc.

BE-32
BIOETHERS

BE-33
BIOETHERS

• BIO-MTBE (methyl-tertiary-buthyl-ether) (eg. from methanol obtained from

bioorigined synthesis gas)

• BIO-ETBE (ethyl-tertiary-buthyl-ether)

• BIO-TAME (tertiary-amyl-methyl-ether)

• BIO-TAEE (tertiary-amyl-ethyl-ether)

BE-34
MAIN PROPERTIES OF BIOETHERS USED IN GASOLINE

Bioether
Property Gasoline
MTBE ETBE TAME TAEE
Molecular weight - 88.15 102.18 102.18 116.2
Density (20°C), g/cm3 0.73-0.77 0.741 0.747 0.770 0.764
Boiling point, °C 30-220 55.2 71.7 86.1 101
Reid Vapor Pressure, 37.8°C, kPa 45-60 53.8 27.6 17.5 17.5
Stochiometric air/fuel mass ratio 14.7 11.8 12.1 12.1 14.4

Research Octane Number 88-98 118 118 110 105

Motor Octane Number 80-88 100 102 97 95
Heating value, MJ/kg 42-44 35.1 36.2 37.6 -
Evaporization heat, kJ/kg 349 337 321 326 227
Solubility in water (20°C), % - 4.3 2.0 1.15 0.4
Mass ratio of biocomponents, % - 36.4 45.1 31.3 39.6

BE-35
CHEMISTRY OF BIOETHER SYNTHESIS
CH3
CH3 O C CH3
+ CH3 OH
biometanol CH3
biomethanol
CH3 bio-metil-tecier-butil-éter
bio-methyl-tertiary-buthyl-ether
CH2 C
CH3 CH3
isobuthylene
izobutilén + CH3 CH2 OH CH3 CH2 O C CH3
CH3
bioetanol
bioethanol
bio-ethyl-tertiary-buthyl-ether
bio-etil-tecier-butil-éter

CH3 CH3
CH2 C CH2 CH3 + CH3 OH CH3 C CH2 CH3
2-methyl-1-butene
2-metil-1-butén biometanol
biomethanol O
CH3
bio-tercier-amil-metil-éter
bio-tertiary-amyl-methyl-ether

CH3 CH3
CH3 C CH CH3 + CH3 CH2 OH CH3 C CH2 CH3
2-metil-2-butén
2-methyl-2-butene bioetanol
bioethanol O CH2 CH3

bio-tercier-amil-etil-éter
bio-tertiary-amyl-ethyl-ether

BE-36
TYPICAL COMPOSITION OF OLEFINIC FEEDSTOCKS I.

Butenes
FCC plant Steam Isobutane Isomerization Fischer-Tropsch
Source cracking dehydrogenation synthesis

Composition, %

isobutane 35 2 52 6 3-5
n-butane 11 5 1 44 6-10
isobutene 15 45 48 17 5-15
1-butene 13 28 1 10 60-80
2-butenes 26 20 0 23 5-15

BE-37
BLENDING OF BIO-ETBE IN TO GASOLINES

• Bio-ETBE blending limit:

– maximum level: 15.0 v/v% (MSZ EN 228:2012+A1:2017;
maximum level of oxygen content: 2.7 %)
– maximum level: 22.0 v/v% (MSZ EN 228:2012+A1:2017;
maximum level of oxygen content: 3.7 %)

• Method of blending: in existing gasoline blending system

BE-38
EFFECTS OF BIO-ETBE

− Effects on gasolines

− Effects on engines

− Effects on structural materials

− Effects on environment

BE-39
EFFECTS OF BIO-ETBE ON THE GASOLINE QUALITY

• Inner oxygen source

• Less water soluble than ethanol

• Decreasing of emission

• Octane number improving

BE-40
EFFECTS OF 10 V/V% MTBE, ETBE AND ETHANOL ON DISTILLATION
CURVE OF GASOLINE

120
110 Alapbenzin
Gasoline
100
°C
Temperature,°C

90
Hőmérséklet,

80 Gasoline +
Alapbenzin
70 10% ethanol
+ 10% etanol
60
50 Alapbenzin
Gasoline + Gasoline +
Alapbenzin
40 + 10%
10%ETBE
ETBE 10% MTBE
+ 10% MTBE

30
0 20 40 60 80 100
Átdesztillált mennyiség,
Distillated volume, V/V%v/v%

BE-41
CHANGING OF REID VAPOR PRESSURE IN CASE OF BLENDING DIFFERENT
ETHERS AND ETHANOL IN TO GASOLINE (RVP OF GASOLINE: 54 kPa)

10
kPakPa

Etanol
Ethanol

5
pressure changing,
Gőznyomásváltozás,

MTBE
0

-5
ETBE

-10
Vapor

TAME
-15 TAEE

0 1 2 3 4
Motorbenzin
Oxygen oxigéntartalma,
content of gasoline, %%

BE-42
 PRODUCTION OF DME

Via methanol
CO + 2 H2 → CH3-OH

2 CH3-OH → CH3-O-CH3 + H2O

Catalyst: amorphous alumina with ca. 10% silica

Directly from synthesis gas

3 CO + 3 H2 → CH3-O-CH3 + CO2
Catalyst: Cu-Zn-Zr-based catalyst on solid acid like g-Al2O3
T = 260-270°C; P = 40-60 bar

DME-43
 MAIN PROPERTIES OF DME AND DIESEL FUEL

Property DME Diesel fuel

Molecular weight 46 208
Carbon content, % 52.2 86.1
Hydrogen content, % 13.0 13.9
Oxygen content, % 34.8 0
Density (liquid), g/cm3 0.668 0.840
Boiling point, °C -25 180-360
Heating value, MJ/kg 27.6-28.8 42.7
Evaporation heat, kJ/kg 412* ~256**
Cetane number 55-65 45-55
Stochiometric air/fuel weight ratio, kg/kg 9.0 14.6
Auto ignition temperature, °C 235 250
Explosion range (gas in the air), v/v% 3.4-18 0.6-7.5
CO2 emission, g/MJ 67.5 74.2

* On 20°C and 5 bar

** On 1 bar

DME-44
 ADVANTAGES OF DME

• Can be produced from fossil and renewable sources – contributing for

energy supply,
• Low auto ignition temperature (high cetane number), can be applied in
Diesel engines; short ignition delay (low degree noise, easy cold start),
• High vapor pressure on low temperature, fast evaporization in the cylinder,
• Low particle formation, low emission (high oxygen content, low
carbon/hydrogen ratio, does not contain C-C bond)
• NOx- and particle emission could be decreased well

DME-45
 DISADVANTAGES OF DME
• Special storage tank and injection method (lower energy content),
• Maximum limit of DME in diesel fuel could be ca. 20% due to its low viscosity,
• DME should be filtered before the injection,
• New type of seals and gaskets should be developed and used,
• Poor lubricity, need for higher concentration of additives,
• Cavitation due to the high vapor pressure, injection could changing,
• Higher energy demand of concentration before the injection

DME-46
Thank you for your kind
attention!

47