Charpter 3

Petroleum
Products
---diesel

Aijun Duan
2020.10
1
 2. Diesel
Diesel is the fuel of diesel engine.

According to the different rotating speed of

diesel engine, they need different types of

diesels：

rotating speed >1000 rpm: light diesel

rotating speed 500～1000 rpm：Heavy diesel

2
 2.1 Operation principle of diesel engine
Diesel engine is also called as

compression ignition engine ， which is usually

used in the agricultural machine、heavy loaded

vehicle 、 railway machine 、 shipping 、

engineering and mining machines.

3
 2.1 Operation principle of diesel engine

2.1.1 Operation principle

Same as the petrol engine, the working

cycle of diesel engine also include four

processes: in-take stroke 、 compression

stroke、expansion stroke and exhaust stroke。

4
 High pressure fuel
injector line
Fuel
injector

Intake Exhaust
• valve valve

5
 Main differences：
（1）compression ratios
Diesel engine is 16 ～ 20 ， the temp. and
pressure of compressed gas are much higher.
500～700℃，3～5MPa
（For petrol engine ：300～450℃，0.7～1.5MPa）

（2）different ignition manners

Diesel engine is self ignition （self ignition

point is 200～250℃）

Petrol engine is spark ignition.

6
（3）different heat efficiencies

Diesel engine is higher than petrol engine,

with same power, the former can save fuels of

20～30％。

2.1.2 Regulations of fuel by the diesel engine

◼Good properties of atomization, volatility
and combustion；
◼Good supply capability of fuels；
◼No corrosion and abrasion to engines；
◼Good storage and heat stability. 7
 2.2 Combustion property of diesel
Good combustion property of diesel means

that the fuel ejected into the combustion

chamber can be mixed well with high

temperature air to form a combustible gas

mixture, and easy to combust totally by self

ignition in a short time.

8
 2.2 Combustion property of diesel

2.2.1 Combustion property

Four periods：

ignition delay, rapid combustion period,

slow combustion period, after combustion
period.

9
 The combustion process
◆The combustion of automotive gas oil(AGO) in
a diesel engine is a rapid oxidation process.
◆The flammable mixture is obtained by injecting
a spray of fuel into compressed air in the
combustion chamber.
◆At the high temperature resulting from
compression of the air, the mixture ignites
spontaneously.
◆Typical compression ratios for automotive
diesel engines are in the range 15:1 to 23:1.
10
Pressure/MPa

Crank angle

Pressure changes in the diesel engines

1-ignition delay; 2-rapid combustion
period; 3-slow combustion period 11
▪Ignition delay（delayed ignition period）：A-
B, the time period from the start of oil
blooming to the ignition and combustion，1～
3ms。
Physical delay ： oil jet 、 atomization 、
heating 、 evaporation 、 diffusion to
combustible gas；
Chemical delay：fuel is heated and start to
proceed a chain reactions of oxidation and
to form some peroxides, then begin to
combust by self ignition as the peroxides
reach at a definite concentration. 12
▪Rapid combustion period ： B-C ， start to
combust with rapid speed until the pressure
can not increase sharply；

▪Slow combustion period : C-D，main stage，

50～60% of fuel are combusted in this stage,
and pressure do not increase sharply until it
is down.

▪After combustion period ： D-E ， pressure

decrease sharply until the combustion stop.
13
 Basic requirement
❖ Ignites spontaneously when injected into
the combustion chamber;
❖ Burns cleanly, quietly and economically in
the engine;
❖ Is suitable for the engine’s injection
equipment;
❖ Does not degrade the efficiency of any
exhaust after-treatment device;
❖ Can be handled safely and conveniently
during distribution;
❖ Does not degrade under normal usage. 14
 Basic
Basic requirement
requirement
❖ Does not harm surface with which it
normally comes into contact
❖ Does not contain contaminants or
separated wax
❖ Specification should be met.
❖ How the composition and properties of
the diesel fuel affect requirements.

15
 The self-ignition point can not be
very low to make sure it not to self-
ignition at the early stage;

The self-ignition point can not be

very high to make sure it easy to
proceed self-ignitions at the right
time.

16
2.2.2 Evaluation factor of diesel

combustion property―Cetane Number

Cetane Number—CN of diesel is tested in

a standard test diesel engine.

Standard Cetane CN＝100

fuels －methyl naphthaline CN=0

17
•CN is lower then diesel fuel is hard to be
combusted and the ignition delay will be long,
resulting in a bad working state of engine；
•CN is high then diesel fuel is easy to be
combusted and the ignition delay will be short,
resulting in a good steady working state of
engine；
•CN is much higher，then the partial section
will be combusted incompletely, and result in
black smog.
High speed engine：40～60;
Middle speed：30～35;
Low speed: <25 18
 2.2.3 The relationship between the
CN and chemical composition
CNs of different types of hydrocarbons
are different, the general rules are as follows:
➢CNs of normal alkanes are the highest, MW,
CN ;
➢CNs of isoparaffine are lower to normal
alkane;
➢Normal olefins have higher CN;
➢CNs of naphthene are low
➢CNs of aromatics are the lowest. 19
 CN of hydrocarbons
Hydrocarbons CN Hydrocarbons CN
n-alkanes naphthenes

Hepane decalin
Octane n-propyldecalin
n-dodecane n-butyldecalin
n-tetradecane sec-butyldecalin
n-hexadecane tert-butyldecalin
i-alkanes n-octadecalin
3-ethyl decane aromatics
4,5-diethyl octane n-hexabenzene

2,2,4,6,6-pentamethyl heptane n-heptylbenzene

7,8-dimethyl tetradecane n-octabenzene

heptamethylnonane n-dodecane

7,8-diethyl tetradecane -methylbenzene

9,10-dimethyl octadecane  -n-butylbenzene

9,10-dipropyl octadecane - tertbutyl benzene

alkenes -n-octabenzene
1-n-tetradecene
1-n-hexadecene
5-butyltetradecene
20
 Self-ignition point ℃

CN
Relationship between CN & self-ignition point

21
 Cetane number

（1.8A + 32)(141.5 - 131.5d 15 .6 )

Diesel index = 15.6
100d1515..66

lg t50
CN Index = 162.41 − 418.51
 20

CN = 442.8 − 462.9d 420

22
 2.3 Volatility of diesel
2.3.1 The effects of volatility on the diesel
engine operation

◆The formation rate of combustible gas

mixture inside the diesel engine depend
on the volatility rate of diesel；

◆The volatility rate is related to the air

temperature of combustion chamber
and the degree of diesel compositions.
23
◆The lighter is the diesel, the rapid is the
volatility rate；

◆If the distillate is too light, the volatility

rate is too rapid, resulting in the pressure of
chamber increase sharply, and making the
engine working unstable.

◆If the distillate of diesel is too heavy, the

volatility is slow, and combust incompletely,
power will decrease and the fuel
consumption increase;
24
 2.3.2 Evaluation factors for volatility
1、BP distillation range
（1）Temp. of 50％
Representing the amounts of light distillates
inside the diesel, which affect on the start-up
ability of diesel engine, in China Temp. of 50％
≯300℃。
T50 >300 ℃ will result in smoke formation in
high-speed engines, if it below 200 ℃ will not
have adequate viscosity and energy content to
give acceptable engine performance.
Low T50 (indicating a light diesel fuel) is
good for cold start and low smoke emissions.
25
 1、BP distillation range
（2）Temp. of 90％&95％
Representing the amounts of heavy
distillates inside the diesel, in China Temp. of
90％≯355℃，95%≯365℃ 。
A high T95 fuel will not burn completely,
resulting in poor fuel economy and higher
emissions.
Too high: the fuel spray will be poor
atomized and poorly burned, power output is
reduced and fuel consumption increased.
Too low: a good volatility result in vapor
locks in the fuel system and poor penetration of
the fuel spray into the combustion chamber. 26
 2、Flash point

To control the volatility of diesel not

too much, flash points of diesel are
stipulated as：

－35#&－50# light diesel FP≮45℃

－20# FP≮ 60℃

others# FP≮ 65℃

FP of diesel is an important factor to

make sure its security in using.
27
 2.4 Fluidity of diesel

2.4.1 Viscosity
Upper viscosity: limit to ensure that fuel
flows readily during cold starting .
lower limit to avoid power loss and problems
with re-starting the engine when it is hot.
Measured: time taken for a given volume of
fuel to flow through a standard capillary tube
at a fix temperature of 20℃ or 40℃, centi-
stoke, mm2/s
Affecting on the start-up and the shape of
the fuel spray. 28
2.4.1 Viscosity
Too high: cause poor atomization and
inadequate mixing with air in the
combustion chamber.
Combustion is incomplete,
resulting in loss of power, increased
fuel consumption and producd black
smoke and hydrocarbon emissions.

29
2.4.1 Viscosity
Unsuitable viscosity of fuel can also
lead to high rates of engine wear.
Too high a viscosity can cause the fuel
spray to strike the cylinder walls, washing
away the lubricant and diluting the oil in
the crankcase.
In the long time, a reduction in the
effectiveness of lubrication leads to
increased rates of engine wear.
30
2.4.1 Viscosity
Too low: produces a spray which does
not penetrate far enough into the combustion
chamber.
This again reduces the efficiency of
combustion due to poor fuel-air mixing,
leading to higher hydrocarbon emissions.
Also injection timing and injected volume
are respectively delayed and reduced due to
leakage in the fuel injection pump system,
which reduces power.
31
2.4.1 Viscosity
Too low a viscosity can also cause
wear problems, particularly in rotary fuel
pumps, which rely entirely on the fuel for
their lubrication.
The lubricating properties of the fuel
tend to decrease with viscosity, so too
low a viscosity can cause wear in the
pump.

32
2.4.2 Cold flow performance
The cold flow performance of diesel
is related to the engine fuel supply,
storage and transportation properties.
（1）solidifying point
（2）Cold filter plugging point(CFPP)
Cold flow performance is related to
the compositions of diesel，the more
content of alkane has a bad fluidity at
low temperature. 33
2.5 Stability, causticity and purity
2.5.1 Stability
Diesel with bad stability will be easy to
change color, even to produce deposits.
Hazards：blocking the oil nozzle and fuel filter
The stability of diesel depend on the
chemical composition, and the unstable
components include: diolefin, polynuclear
aromatics, sulfide and nitride compounds.
Evaluation factors ： sediment and carbon
residue on 10 percent residuum.
34
2.5.2 Causticity
The main components affected on
the diesel causticity are the sulfur
compounds in diesel, especially the
active sulfides, i.e., mercaptan.
Thus, the diesel specification
stipulated the sulfur and mercaptan
contents in diesel.
Besides，no watar soluble acid and
base are permitted in diesel. 35
2.5.3 Purity

The most important factors affected on

the purity of diesel are water and
mechanical impurity. The former will have
effects on the heat value and low-
temperature property of diesel; and the
latter will block the fuel pipeline and
deteriorate to the abrasion of engine parts.

Resources ： brought in the processes of

storage, transportation and filling-up. 36
 2.6 The history of world fuel
specification of diesel

World fuel specification of diesel Ⅱ

Projects Quality specification

CN 53

S, %（m ） 0.03

Aromatics，% （m） 25

Poly arom., %（v） 5

T95％/℃ 355

37
World fuel specification of diesel Ⅲ

Projects Quality specification

CN 55

S, %（m） 0.003

Aromatics，%（m） 15

Poly arom，%（v） 2

T95％/℃ 340

38
 World fuel specification of diesel

Projects I# II# III# IV#

CN ≮ 48 53 55 55
CN index ≮ 45 50 52 52
95％, ℃ ≯ 370 355 340 340
FBP ， ℃ ≯ 365 350 350
d，kg/m3(15℃) ≯ 820－860 820－850 820－840 820－840

S％（m/m) ≯ 0.5 0.03 0.003 0

Aromatics ％（m/m) ≯
Total 25 15 15
Poly arom 5 2 2

39
 2.7 The history of China fuel
specification of diesel

2.7.1 Diesel fuel grades and brands

Light diesel：SP: 10#、0#、－10#、

Diesel －20#、－35# and －50#

Heavy oil：50℃: 10#、20#、30#

40
 2.7 The history of China fuel
specification of diesel

Table 2 China fuel specification of

diesel in 2000（GB252－94）
Projects
premium Grade A acceptable

CN ≤45

S, %（m） ≤0.2 ≤0.5 ≤1.0

Aromatics, %（m） -

Poly aroma, %（v） -

T95％ /℃ ≤365 41
 Diesel specification and test methods（ GB/T 19147-2003）
Projects 10# 5# 0# -10# -20# -35# -50# Test method

Antioxidation stability SH／T 0175

Insoluable content, (mg／100 mL) ≯ 2.5

S, m％ ≯ 0.05 GB／T 380

Carbon residua on 10％distillation,m％ ≯ 0.3 GB／T 268

Ash content m％ ≯ 0.01 GB／T 508

Copper strip corrosion (50℃，3 h)／ ≯ l GB／T 5096

Diesel specification Water content, v％ ≯ Trace GB／T 260

and test methods Impurity Zero GB／T 511

GB/T 19147-2003
Lubricity, corrected wear scar 1SO 12156—1

diameter @60℃/μm ≯ 460

2
Viscosity @ 20℃／(mm ／s) 3.0～8.0 2.5～8.0 1.8～7.0 GB／T 265

Solidifying point／℃ ≯ 10 5 0 -10 -20 -35 -50 GB／T 510

Cold filter plugging point／℃ ≯ 12 8 4 -5 -14 -29 -44 SH／T 0248

S%=0.015 Flash point／℃ ≮ 55 50 45 GB／T 261

Cetane number
Ignitability (to meet one of )

CN ≮ 49 46 45 GB／T 386

Freezing Point Or CNI ≮ 46 46 43 GB／T 11139

SH／T 0694

Cold Filtering Projects 10# 5# 0# -10# -20# -35# -50# Test method

Point Distillation range

Temp.50％／℃ ≯ 300
GB／T 6536

Viscosity Temp.90％／℃

Temp.95％／℃
≯

≯
355

365
3
Density @ 20'℃／(kg／m ) 820~860 800~840 GB／T 1884
42
GB／T 1885
 Diesel specification and test methods from 2005.7.1

Quality specification Test

Projects
5# 0# -10# -20# -35# method
Chromaticity, ≯ 3.5 GB/T 6540

Diesel oxidation stability，

Insoluable content, mg/100mL ≯
2.5 SH/T 0175

specification GB/T 380,

Sb，%（m） 0.035 ASTM
and test
≯
D4294

methods in Acidity， mgKOH/100mL ≯ 7 GB/T 258

2005
Carbon residua on 10％distillation,m％ ≯ 0.3 GB/T 268
Ash content m％ ≯ 0.01 GB/T 508
Copper strip corrosion (50℃，3 h)／ ≯ 1 GB/T 5096
Water content, v％ ≯ Trace GB/T 260
Impurity zero GB/T 511

3.0～8.0 2.5～8.0 1.8～7.0 GB/T 265

S%=0.035
Viscosity @ 20℃／(mm2／s)

Solidifying point／℃ ≯ 5 0 -10 -20 -35 GB/T 510

Cetane number
Cold filter plugging point／℃ ≯ 8 4 -5 -14 -29 SH/T 0248
Freezing Point
Flash point／℃ ≮ 55 GB/T 261
CN 51 49 47 GB/T 386
Cold Filtering Point ≮
GB/T 11139
CN index e ≮ 46 46 46
Viscosity SH/T 0694
BP range：
Polyaromatics,11%(m/m)
T50%，℃ ≯ 300
GB/T 6536
T90%，℃ ≯ 355
T95%，℃ ≯ 365

Poly arom ％（m） ≯ 11 SH/T 0606

Lubricityf WSD µm ≯ 460 ISO 12156-1

43
GB/T 1884
d（20℃）kg/m3 820～845 800～840
GB/T 1885
 China diesel fuel specification and test methods

Quality regulations Test methods

Type
# # # # #

Chromaticity, ≯

antixidation,
Insoluble material ≯

S, ≯

Acidity, mgKOH/100mL ≯
Carbon residua on 10％distillation,m％ ≯

Ash content m％ ≯

Copper strip corrosion (50℃，3 h)／ ≯

Water content, v％ ≯ Trace

Impurity Zero

44
 Viscosity @ 20℃／ mm2／s

Solidifying point／℃ ≯

Cold filter plugging point／℃ ≯

FP(Closed up) ≮

CN ≮

CNI ≮

Distillation range
Temp.50％／℃ ≯
Temp.90％／℃ ≯
Temp.95％／℃ ≯

Poly arom. ≯
Lubricity, corrected wear scar diameter @60℃/μm
≯

Density @ 20'℃／(kg／m3)

45
 China diesel fuel specification
National IV

Standards
Test
Properties
methods

Flash point ≮

Density @ 20'℃／(kg／m3)
S, ≯
Acidity, mgKOH/100mL ≯
CN, ≮
CNI, ≮
Lubricity, De(60℃)／μm ≯

Poly arom, m％ ≯
FAME(Fatty Acid Methyl Ester)m％ ≯

46
 China diesel fuel specification
National V

Standards

Properties Test
methods

Flash point ≮

Density @ 20'℃／(kg／m3)

S, ≯

Acidity, mgKOH/100mL ≯

CN, ≮
CNI, ≮
Lubricity, De(60℃)／μm ≯

Poly arom, m％ ≯
FAME(Fatty Acid Methyl Ester)m％ ≯

47
 China diesel fuel specification
National VI
Standards
Properties Test
methods

Antixidation,
Insoluble material, mg/100mL ≯

S, mg/kg ≯

Acidity, mgKOH/100mL
≯
Carbon residua on 10％distillation,
m％ ≯

Ash content m％ ≯
Copper strip corrosion (50℃，3 h)／ ≯
Water content, v％ ≯

Lubricity, De(60℃)／μm ≯

Lubricity, De(60℃)／μm ≯

Poly arom, m％ ≯

Viscosity @ 20℃／ mm2／s

Solidifying point／℃ ≯
Cold filter plugging point／℃ ≯
FP(Closed up) ≮
48
 2.8 The development of diesel
additives
• Classification
• Consumptions of diesel additives
• Diesel detergent additives
• Lubricity aids additives
• Low temp. fluidity improvement additives
• CN improvement additives
• Combustion-aiding additives
 2.8.1 Classifications
Additives dose rates/t

Anti-foam additives

• Antistatic additives(ASA)
Class
Antirust

Metal deactivator
additives(MDA)
CN improver

Low temp. fluidity improver

detergent additive

Dyestuff indicator

anti flocculant

ASA

Anti-oxidant
Alkyl amine phosphate ester, aliphatic acid amine

combustion-aids
 2.8.2 Consumptions of diesel
additives in 1998
•
Additives dose rates/104t (%) Value/108USD(%)

Gasoline detergent additive

Low temp. fluidity improver

CN improver

Anti-oxidant

Anti-knock additives

Lubricity aid additives

Preservative

Anti-icing additive

Other additive

Total
52
53
 2.8.3 Diesel detergent additives

❑ IDI(Indirect injector) system:

➢ deposits;

Effects of coke in injector on fuel consumption & emission

Clean injector Coked injector Increase/%
Additives

PM

Fuel consumption
 Effects of diesel detergent additives(DDA) on fuel stability

Samples Deposit Resin Total

undissolved
Diesel 1
Diesel 1+DDA 100 g/g
Diesel 2
Diesel 2+DDA 100 g/g
Diesel 3
Diesel 3+DDA 100 g/g

• Main brands：
Chevron---OFA278, OFA425B;
Ethyl---Hitec4235, Hitec4301,
Hitec4302,
Du pont---FOA-2 etc.
dose rates of 0.01%~0.02%.
 2.8.4 Lubricity aids additives

• To improve the Lubricating ability of

diesel engine injector system;
• Classification of lubrication additive:

aromatic acylamide(酰胺)
aromatic amine
alcohol amine
etc
2.8.4 Lubricity aids additives

Commercial brands:
Ethyl---Hitec515, Hitec580,
Hitec4848A
Du pont---DCI-4A, DCI-6A,
Mobil---Mobiland F-800,
Lubrizol---LZ539S
etc
 2.8.5 Low temp. fluidity
improvement additives

Classification of low temp. fluidity

improvement additives:
➢ Anti nepheloid additives

➢ Pour-point depressants

➢ Wax dispersant

➢ etc

Nepheloid: 雾状的; depressants: 抑制剂; dispersant: 分散剂

 2.8.5 Low temp. fluidity
improvement additives

Classification of chemicals
No Name Description
Ethene-acetic ethene ester polymer
Exxon---Paradyne 20, 25, 26, 27, ECA5920,

Dibutyl acylmide acid 5966 etcOFA411 etc

Chevron---OFA410,
Ethene-crylic acid ester polymer Amoco---AmocoA543
Acetic ethene-butylene diacid ester polymer BASF---Keroflux M
Polyvinyl chloride Petrolite---Toled T35
 Brands of low temp. fluidity improvement
additives
Country Co. Brand Description

Ethene-acetic ethene ester polymer

Ethene-crylic acid ester polymer

Dibutyl acylmide acid

USA

Polyvinyl chloride

Ethene-acetic ethene ester polymer

Ethene-acetic ethene ester polymer

Ethene-acetic ethene ester polymer

USSR
Sanyo Ethene-acetic ethene ester polymer
Japan
Ou -olefin-anhydride polymer

German Acetic ethene-butylene diacid ester po

y
France IFP
 min
1 10
8

Lowest temp. to enable diesel engine in

6
4
2
0
-2
-4
-6
-8
-10
-12
-14

Additive Base Aether

nitric
acid
2,2- Propylene Organic
dinitro peroxide peroxide
fuel amyl propane mixture
CC 85% ester
Dose/m% SR 15% 10 1.0 1.0 1.0 5.0

CN 36 41.5 47 48.5 37.1 53

 2.8.6 CN improvement additives

• Components: alkyl nitric acid ester---

isooctyl nitric acid ester;
• Main brands and properties of CN additives

Brand Comp. Purpose Dose rates/ Co.

m％
ECA alkyl nitric acid Diesel 0.1~0.2 Exxon
8478 ester Co.
ECA nitric acid amyl Diesel 0.1 Exxon
8472 ester Co.
Hitec Multi-alkyl Diesel 0.1~0.2 Ethyl Co.
4102 nitric acid ester
 Effects of CN additives on CN
improvement
Additive Initial CN Dose/v% After CN  CN
Nitrobutane 31.0 1.0 45.4 14.1
Nitrooctane 46.0 2.2 49.8 3.8
nitric acid
acetic ester 55.0 2.0 74.0 19.0
nitric acid
amyl ester 44.0 1.5 67.0 23.0
nitric acid
butyl ester 44.0 1.5 63.0 19.0
aldehyde 39.1 1.5 42.6 3.5
aether 39.1 1.5 39.9 -0.2
 2.8.7 Combustion aids
additive(CAA)
• To control the deposit pollutants;
• Main components: organic compounds
of barium, calcium, magnesium and
iron.
• LZ565 developed by Lubrizol co. is a
barium combustion aids additive, the
barium content is 20％～25％ and its
dose rate is 0.25％～0.50％. As the dose
rate is 0 . 5 0 ％ , the exhaust aerosol
reduces 30 units.
Aerosol: 气溶胶
 Brands of CAA

Brand Composition
d/ / FP/
S/% Ba/% Mg/% N/% Co.
g·cm-3 mm3·s-1 ºC
Mobilad Organic metal 30.1 Mobil
compounds 1.02 74 - 22.5 -
F-697 (38ºC) Co.
High basicity 9.6 Lubrizo
LZ565 sulfonic barium 1.22 - 0.25~0.5 20~25 - 0.4~0.6
(100ºC) l Co.
Magnesium 1.65 Lubrizo
LZ8220 organic 0.935 - - - 4~47 0.3
compounds (40ºC) l Co.
Magnesium
Lubrizo
LZ8058 organic 1.3 - 75 0.4~1.2 - 20~22 -
compounds l Co.
Bryton
Witco
Brium - - - - - 27 - -
Co.
190
 Multifunctional additives
Multifunctional:
• Composites of antioxidation, deter-
gent, metal passivator, antirusting
additives, combustion aids, & CN
improvement additives.
• Main brands：
➢ Ethyl---Hitec4201, 4202, 4235;

➢ Du pont FOA-408, FOA-12 etc。