SIST-TP CEN/TR 17103:2017

SLOVENSKI STANDARD
SIST-TP CEN/TR 17103:2017
01-september-2017
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Fast pyrolysis bio-oil for stationary internal combustion engines - Quality determination
Pyrolyseprodukte - Schnell Pyrolyse-Bio-Öle für stationäre Verbrennungsmaschinen -
Qualitätsbezeichnung
Pétrol et produits rélatives - Huiles biologique de pyrolyse rapide pour application en
moteurs stationés avec combustion interne - Désignation de qualité
Ta slovenski standard je istoveten z: CEN/TR 17103:2017
ICS:
75.160.40 Biogoriva Biofuels
SIST-TP CEN/TR 17103:2017 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST-TP CEN/TR 17103:2017

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SIST-TP CEN/TR 17103:2017


CEN/TR 17103
TECHNICAL REPORT

RAPPORT TECHNIQUE

May 2017
TECHNISCHER BERICHT
ICS 75.160.40
English Version

Petroleum and related products - Fast pyrolysis bio-oils
for stationary internal combustion engines - Quality
determination
Pétrol et produits rélatives - Huiles biologique de Pyrolyseprodukte - Schnell Pyrolyse-Bio-Öle für
pyrolyse rapide pour application en moteurs stationés stationäre Verbrennungsmaschinen -
avec combustion interne - Désignation de qualité Qualitätsbezeichnung


This Technical Report was approved by CEN on 11 April 2017. It has been drawn up by the Technical Committee CEN/TC 19.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and United Kingdom.





EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2017 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 17103:2017 E
worldwide for CEN national Members.

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Contents Page
European foreword . 3
Introduction . 4
1 Scope . 5
2 Normative references . 5
3 Terms and definitions . 6
4 Sampling and sample handling . 7
5 Requirements and test methods . 8
5.1 General . 8
5.2 FPBO properties affecting internal combustion engines . 9
5.2.1 Water content . 9
5.2.2 Net calorific value . 9
5.2.3 pH . 10
5.2.4 Viscosity . 10
5.2.5 Density . 10
5.2.6 Pour point . 10
5.2.7 Nitrogen content . 10
5.2.8 Sulfur . 10
5.2.9 Solids . 10
5.2.10 Ash content . 10
5.2.11 Flash point . 11
5.2.12 Alkali and alkali earth metals . 11
5.2.13 Chlorine . 11
5.2.14 Cetane number . 11
5.2.15 Additives . 11
5.3 Proposed general requirements for stationary internal combustion engines . 11
6 Plan to upgrade this Technical Report to Technical Specification . 13
Annex A (informative) Storage of fast pyrolysis bio-oil . 14
Annex B (normative) Compatible materials . 15
Annex C (informative) Cetane number . 16
Annex D (normative) Information on test method procedures . 18
Bibliography . 20

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European foreword
This document (CEN/TR 17103:2017) has been prepared by Technical Committee CEN/TC 19 “Gaseous
and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin”, the
secretariat of which is held by NEN.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN shall not be held responsible for identifying any or all such patent rights.
This document has been prepared under a mandate [1] given to CEN by the European Commission and
the European Free Trade Association.
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Introduction
The European Union is promoting the use of renewable energy. Liquid biofuels have rarely been used
for CHP applications with the exception of vegetable oils which in some cases have been used in
combined heat and power (CHP) applications and several boiler manufacturers promote its use.
However, given the demand for biodiesel for the transport sector little uptake has been reported for
biodiesel in the CHP sector. Hence the European Commission (EC) requested CEN to develop a
'Technical Specification for a quality specification for pyrolysis oil replacing fuel oils in stationary
internal combustion engines' [1].
Fast pyrolysis bio-oils (FPBO) or fast pyrolysis liquids are completely different from conventional fossil
fuels both in their physical properties and chemical composition. They are brownish liquids with a
distinct and smoky odour. They can be produced from woody biomass [3] and agrobiomass
(herbaceous [3]) and there is a wide range of reactor types suitable for fast pyrolysis bio-oil production.
Contrary to fossil fuels, they are highly polar, mainly water-soluble containing typically about
25 % (m/m) (on wet basis) water, are acidic in nature, dense, and viscous liquids, very poorly or not
miscible with hydrocarbons [4].
CEN adopted work item 00019499 for the requested work and installed CEN/TC 19/WG 41 'Pyrolysis
oil' to develop the CEN Technical Specification. During its work the group encountered the following:
• FPBO is not yet commercialized for stationary internal combustion engines (ICE) and there is
neither enough data on the properties for FPBO for ICE use and parameters to determine
combustion properties are not fully understood. Also the long-duration tests in ICE have not yet
been carried out.
• WG 41 performed an enquiry within the leading engine manufacturers to collect data and proposals
for threshold values. Most of the manufacturers did not have experience with FPBO. Several
comments made by the manufacturers was that further research and development work was
required on several issues (e.g. type of fuel injection system, chemical resistance, effect of
solids/char content of bio-oil on erosion/corrosion at fuel nozzles, and ignition properties).
• There are several important properties (e.g. combustion properties, flash point and chlorine) that
should be incorporated as grade criteria, but no established test methods for fast pyrolysis bio-oil
are available. Research and development is needed to develop these methods to be used for
specification of FPBO for ICE.
WG 41 thus proposed to CEN/TC 19 to draft a Technical Report (TR) instead of a Technical
Specification, which was approved [2] and thereafter adopted by the CEN/BT and accepted by the EC.
This document is laying down the outcome of the study and the quality that so far has been found
acceptable for ICE. Further investigations and market application should be continued in order to
decide to eventually revise this document into a deliverable originally requested by the EC.
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1 Scope
This Technical Report describes the key properties of fast pyrolysis bio-oils and their importance to the
fuel quality for use in stationary internal combustion engines.
Internal combustion engine (ICE) in the scope of this document means a type of engine in which heat
energy and mechanical energy is produced inside the engine. ICE include compression ignition engines
(diesel engines) and gas turbines.
Attention is drawn to differences especially in those properties, which can have an effect on the
required engine performance, such as ash, acidity, viscosity, combustion properties, and sulfur content.
In addition to the quality requirements and related test methods for FPBO, further instructions on
storage (Annex A), sampling (Clause 4), and materials compatibility (Annex B) are given.
NOTE For the purposes of this Technical Report, the terms “% (m/m)” and “% (V/V)” are used to represent
the mass fraction (µ) and the volume fraction (φ) of a material, respectively.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated
references, the latest edition of the referenced document (including any amendments) applies.
EN 16476, Liquid petroleum products - Determination of Sodium, Potassium, Calcium, Phosphorus, Copper
and Zinc contents in diesel fuel - Method via Inductively Coupled Plasma Optical Emission Spectrometry
(ICP OES)
EN 16900:2017, Fast pyrolysis bio-oils for industrial boilers - Requirements and test methods
EN ISO 2719, Determination of flash point - Pensky-Martens closed cup method (ISO 2719)
EN ISO 3104, Petroleum products - Transparent and opaque liquids - Determination of kinematic viscosity
and calculation of dynamic viscosity (ISO 3104)
EN ISO 3170:2004, Petroleum liquids - Manual sampling (ISO 3170:2004)
EN ISO 6245, Petroleum products - Determination of ash (ISO 6245)
EN ISO 8754, Petroleum products - Determination of sulfur content - Energy-dispersive X-ray fluorescence
spectrometry (ISO 8754)
EN ISO 9038, Determination of sustained combustibility of liquids (ISO 9038)
EN ISO 12185, Crude petroleum and petroleum products - Determination of density - Oscillating U-tube
method (ISO 12185)
EN ISO 20846, Petroleum products - Determination of sulfur content of automotive fuels - Ultraviolet
fluorescence method (ISO 20846)
ISO 3016, Petroleum products — Determination of pour point
ASTM D93, Standard Test Methods for Flash Point by Pensky-Martens Closed Cup Tester
ASTM D4294, Standard Test Method for Sulfur in Petroleum and Petroleum Products by Energy Dispersive
X-ray Fluorescence Spectrometry
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ASTM D5291, Standard Test Methods for Instrumental Determination of Carbon, Hydrogen, and Nitrogen
in Petroleum Products and Lubricants
ASTM D5453, Standard Test Method for Determination of Total Sulfur in Light Hydrocarbons, Spark
Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by Ultraviolet Fluorescence
ASTM D7579, Standard Test Method for Pyrolysis Solids Content in Pyrolysis Liquids by Filtration of Solids
in Methanol
ASTM E70, Standard Test Method for pH of Aqueous Solutions With the Glass Electrode
ASTM E203, Standard Test Method for Water Using Volumetric Karl Fischer Titration
DIN 51900-1:2000, Testing of solid and liquid fuels — Determination of gross calorific value by the bomb
calorimeter and calculation of net calorific value — Part 1: Principles, apparatus, methods
DIN 51900-3, Testing of solid and liquid fuels — Determination of gross calorific value by the bomb
calorimeter and calculation of net calorific value — Part 3: Method using adiabatic jacket
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
agrobiomass
biomass obtained from energy crops and/or agricultural by-products (agricultural residues)
[SOURCE: FAO unified bioenergy terminology [UBET]; modified]
3.2
fast pyrolysis
thermal treatment of lignocellulosic biomass at short hot vapour residence time (typically less than 5 s)
typically at between 450 °C–600 °C and at near atmospheric pressure or below, in the absence of
oxygen, using small (typically less than 5 mm) dry (typically less than 10 % (m/m) water) biomass
particles
Note 1 to entry: Under REACH it is defined as “lignocellulosic biomass, at short hot vapour residence time
(typically less than about 10 s) typically at between (450-600) °C at near atmospheric pressure or below, in the
absence of oxygen”.
3.3
fast pyrolysis bio-oil
FPBO
liquid produced by fast pyrolysis from biomass
Note 1 to entry: The typical yield of bio-oil is 60 % (m/m) - 75 % (m/m) on wet basis (energy basis) and
55 % (m/m)– 65 % (m/m) of organic matter. Other products are char and non-condensable gases.
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3.4
solids
solid particles which are not soluble in methanol-dichloromethane (1:1), possibly containing inorganic
elements including sand, char, and additional insoluble organic material
Note 1 to entry: The solids will in time settle to the bottom or raise up to the surface depending on their density
and the fast pyrolysis bio-oil composition.
3.5
stability
situation in which physico–chemical properties remain unchanged during handling and storage
Note 1 to entry: FPBOs are not chemically or thermally as stable as conventional petroleum fuels due to the
high content of reactive oxygen containing compounds and low-boiling volatiles. The instability of FPBOs can be
observed via an increase in viscosity (“aging”) and possible phase-separation by time and temperature. A stability
test based on viscosity increase at 80 °C in 24 h may be used to predict if the bio-oil will stand for a year's storage
at room temperature without phase-separation [4].
Note 2 to entry: Physico-chemical properties remain unchanged during handling and storage at a temperature
close to 20 °C (storage stability) for a long time (i.e. a few months) or when heated at moderate temperature, i.e.
lower than 100 °C, for a short time, i.e. less than one day [23].
4 Sampling and sample handling
It is strongly advised to review all intended test methods prior to sampling to understand the
importance of sampling technique, and special handling requirements for fast pyrolysis bio-oils.
Samples shall be taken as described in EN ISO 3170 and/or in accordance with the requirements of
national standards or regulations for the sampling of FPBO.
Some procedures in EN ISO 3170 are not relevant with fast pyrolysis bio-oils; FPBO is mostly water-
soluble (approximately 80 %) and hence does not include any free water:
— sampling methods described in EN ISO 3170:2004, Clause 8 are not relevant for FPBO;
— for verification of mixing efficiency application of the procedure as described in EN ISO 3170:2004,
9.3.2 is not recommended;
— water content determination should only be carried out according to ASTM E203.
The samples shall be taken immediately after mixing (see Annex A for further instructions).
If bio-oil samples are not analysed immediately, samples should be stored in a freezer [4, 5, 6, 15, 16,
17].
It is pointed out that the sampling devices, sample bottles, and other devices in contact with bio-oil shall
be compatible with bio-oil (see Annex B). Bio-oil shall be well mixed when transferring from the
primary sampling process and/or container to another container and/or analytical apparatus.
Minimum of two samples should be taken and the maximum difference of the viscosity shall not
exceed ± 5 % at 40 °C [6]. A minimum of 0,1 L sample size is recommended.
The bio-oil shall be properly mixed and analysed according to the recommended standard methods. The
bio-oil shall not be filtered or preheated above 40 °C for more than 30 min even though mentioned in
some of the analysis standards. FBPO can typically be analysed like single-phase bio-oils because the
separation of extractive-rich layer is very slow. However, the sampling and analyses should be carried
out immediately after sample homogenization.
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5 Requirements and test methods
5.1 General
FPBO is not yet commercialized for stationary internal combustion engines (ICE) and there is not
enough data on properties for neither engine use nor the long-duration tests in internal engines.
Contrary to fossil fuels, FPBOs are highly polar, mainly water-soluble containing typically about
25 (% (m/m) on wet basis) of water, acidic in nature, dense, and are viscous liquids with a moderate to
high level of viscosity at 40 °C, very poorly or not miscible with hydrocarbons [4]. A typical range for
FPBO characteristics is shown in Table 1.
Table 1 — Typical range of characteristics of fast pyrolysis bio-oils
Property Typical range Unit
Gross calorific value, wet basis [8] 14–19 MJ/kg
Net calorific value, wet basis [8] 13–18 MJ/kg
Water content, wet basis [8] 20–30 % (m/m)
pH [8] 2–3 -
Total acid number (TAN) [8] 70–100 mg KOH/g
2
Kinematic viscosity at 40 °C [8] 15–40 mm /s
3
Density at 15 °C [8] 1,11–1,30 kg/dm
Pour point [8] –9–36 °C
a
Carbon, d.b. [8] 50–60 % (m/m)
Total hydrogen, d.b. [8] 7–8 % (m/m)
Nitrogen, d.b. [8] < 0,5 % (m/m)
Sulfur, d.b. [8] < 0,05 % (m/m)
Oxygen, d. b. [8] 35–40 % (m/m)
Solids, wet basis [8] < 1 % (m/m)
Carbon residue, wet basis [8] 17–23 % (m/m)
Ash, wet basis [8] < 0,3 % (m/m)
Flash point [8] 40–110 °C
Sustain combustibility [8] does not sustain combustion -
Na, K, Ca, Mg. d.b. 0,05–0,2 % (m/m)
Chlorine 75–500 ppm
100
a
d.b. is on dry basis. The change from wet basis (ar) to dry basis (d.b.) follows:
100− M
ar
100− M
ar
Dry basis (d.b.) to wet basis (ar): where M is water content on wet basis
ar
100
(% (m/m)).
WG 41 carried out enquiry within leading engine manufacturers to collect data and proposals for
threshold values. Most of the manufacturers do not have experience of FPBO.
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Several comments stated by manufacturers expressed that further research and development is
requested before fuel quality specification can be drafted. The following issues were given as examples
(see also Tables 2 and 3):
• type of fuel injection system,
• chemical resistance,
• effect of solids/char content of bio-oil on erosion/corrosion at fuel nozzles.
There are several important properties (e.g. combustion properties, flash point and chlorine) that
should be incorporated as grade criteria that do not have established test methods for FPBO. Research
and development is needed to develop these methods to be used for specification of fast pyrolysis bio-
oil for ICE.
5.2 FPBO properties affecting internal combustion engines
5.2.1 Water content
Typically, the water content of the bio-oils is high (>20 % (m/m), on wet basis). Many of quality
parameters correlate inversely with the water content, such as density, viscosity, and net calorific value.
The density, viscosity, and net calorific value increase, when water content decreases. Water content
also informs about the stability and phase separation tendency of FPBO [15]. A 30 % (m/m) limit for
water content is recommended to ensure that no phase separation takes place. However, some bio-oils
with water content above 30 % (m/m) are in one phase due to different chemical composition. A
minimum water content is not needed as the maximum viscosity is proposed to specify. For ICE, a lower
water content limit (≤25 % (m/m)) is proposed to avoid phase separation [18].
5.2.2 Net calorific value
Net calorific value is analysed according to DIN 51900-3 and the calculation of net calorific value at
constant pressure (H ) for moist fuel is specified in DIN 51900-1:2000, Clause 15 (see Formula (1)):
u,p
H = H – [k*·H + 0,8 *(N + O) + k *ω] (1a)
u,p o,v 1
N + O = 100 – [ω + A + C + H + S] (1b)
where
H is gross calorific value at constant volume
o,v
k is the heat of evaporation taking account of the volumetric work performed by the water
formed by the hydrogen during combustion at 25° C (23,7 J/g (as water) or 212 J/% (as
hydrogen), or more exactly 23,7278 J/g and 212,1265 J/% respectively
k is the specific heat of evaporation of water at constant pressure at 25 °C (24,4 J/%)
1
ω is analytical moisture content of the moist fuel, as a percentage of mass;
A is the ash content of the moist fuel, as a percentage by mass
C is the carbon content of the moist fuel, as a percentage by mass
H is the hydrogen content of the moist fuel (excluding hydrogen in water part of fuel), as a
percentage by mass
S is the sulfur content of the moist fuel, as a percentage by mass
N is the nitrogen content of the moist fuel, as a percentage by mass
O is the oxygen content of the moist fuel, as a percentage by mass
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5.2.3 pH
The acidity of FPBO is mainly due to volatile acids, mainly acetic and formic acid, but also due to
phenolics. The acidity can be determined as pH or as TAN (total acid number). For fast pyrolysis bio-oils
it is recommended to measure the acid number as CAN (carboxylic acid number) and PN (phenolic
number). The pH is a representation of how corrosive the oil may be. The pH is typically > 2,0 for bio-
oils. Suitable materials for bio-oils are listed in Annex B.
5.2.4 Viscosity
Viscosity of FPBO is an important property for proper atomization of the FPBO. Typical value used for
stationary diesel engines is a maximum of 17 cSt at feeding temperature and similar values are to be
expected for gas turbine operation. Viscosity of bio-oil is a function of water content and temperature.
The strong decrease in kinematic viscosity with increasing temperature (short-duration) is seen for
various FPBO´s. For ICE a maximum fuel preheat temperature of below 60 °C is recommended, and this
corresponds to around 50 cSt at 40 °C. An automatic system is very sensitive to air bubbles. The sample
shall be carefully mixed by rotating the bottle and then let to stand to remove the air bubbles. Usually
pyrolysis oil does not cause any problems with the detector, but it is possible that no value can be
reported due to the presence of air bubbles. It is recommended to clean the glassware several times
with methanol until effluent is clear. The final cleaning should be carried out with acetone and then air
drying.
5.2.5 Density
3 3
Density of FPBO (measured at 15 °C) is high (1 150 kg/m to 1 250 kg/m ) compared to heavy fuel oil
3 3
(940 kg/m to 1 010 kg/m ). Density correlates with bio-oil water content. If water content is low,
3 3
density may even exceed 1 250 kg/m , and therefore the limit is recommended < 1 300 kg/m .
5.2.6 Pour point
The pour point of FPBO is an indication of the lowest temperature at which the FPBO is capable of
flowing under very low forces. The chemical composition of bio-oil determines the pour point. Based on
experience it is recommended to keep the liquid temperature above – 9 °C for pumping.
5.2.7 Nitrogen content
NO emissions are mainly dependent on nitrogen content and combustion conditions. Nitrogen content
x
of FPBO varies based on the raw material of the oil, it can be 0,1 % (m/m) to < 0,5 % (m/m). At least
triplicates for single determination is recommended (sample is weighted just before analysis). Due to
the small sample size used in the analysis method, the reproducibility of the elemental analysis is
dependent on the homogeneity of FPBO. The detection limit for Nitrogen is typically 0,05 % (m/m).
5.2.8 Sulfur
All fuel-bound-sulfur is converted into SO . Sulfur contents of FPBOs from pine sawdust or forest
x
residue are typically 100 ppm – 300 ppm (0,01 % (m/m) – 0,03 % (m/m)), the highest are when FPBO is
produced from forest residues and lowest from broadleaf and pine sawdust. All sulfur in the raw
material ends up in flue gases. For ICE sulfur content < 0,05 % (m/m) is recommended.
5.2.9 Solids
Solids can contain ash and char. Char is fine carbonaceous powder that cyclones cannot remove from
biomass vapours during pyrolysis. The main particle size of this char is (5–10) μm.
5.2.10 Ash content
Ash content is the amount of non-combustible material in FPBO. Most part of the ash originates from
the biomass feedstock. Ash may also include some sand, silicon oxide (SiO ). Ash-forming materials may
2
be present in two forms, solid particles or water soluble metallic compounds, or both. A high ash
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content of biomass especially agrobiomass leads to bio-oils with a higher water content and lower oil
yield. High ash content also effect on the yield organics and phase separation tendency of FPBO [17].
5.2.11 Flash point
Flash point is not included in the proposed quality table as the test method for flash point has been
proven to be unsuitable for FPBOs as shown by the ILS results (see EN 16900:2017, Annex C). FPBOs
are incapable of sustaining combustion and therefore they can be classified as non-flammable
liquids [18]. Also, according to research [17, 18, 20] FPBO is considered to be a non-flammable liquid.
5.2.12 Alkali and alkali earth metals
Alkali and alkali earth metals like Na, K, Ca and Mg can cause hot corrosion and surface fouling.
Turbines are sensitive to alkalis as they deposit on turbine blades and cause unbalances. The amount of
alkali metals should be as low as possible.
5.2.13 Chlorine
The presence of chlorine in FPBO can lead to formation of unwanted compounds like phosgene with
phosphorus. With alkali metals, chlorine can also participate in hot corrosion. The chlorine level for the
ICE application was selected based on published data on gas turbine demands. There is not yet
consensus on appropriate test method for chlorine determination. Chlorine can be analysed using
colorimetric titration using XPLORER equipment. No standard is available. VTT has developed this
method. The validation of the method with chlorine addition gave a R
...