Study of Calorific Value Analysis

6th CKIC Overseas Training

Seminar Changsha, China
Presented by CKIC-Damon Zhu

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Catalogue
1 Basic Theory of Calorific Value
2 Requirements and Procedures
3 Notes and Maintenance

4 Comparison and Application

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Basic Theory
What is Calorific Value?
The heat produced by combustion of a unit quantity of a substance
(usually a fuel or food) under specified conditions, short for CV.
Gross Calorific Value (GCV)
The heat produced by complete combustion of a substance at constant volume,
all water formed to liquid.

Net Calorific Value (NCV)

The heat produced by combustion of a substance at constant pressure,
all water formed as vapor.

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Basic Theory

Importance of CV
The Calorific Value is a crucial characteristic for each substance

Can be used for payment purpose of fuels. e.g. coal, coke,

biomass

$/ton

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Basic Theory

Importance of CV
Calorific Value decides Price.

Higher calorific value, higher price

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Basic Theory

Importance of CV

2000ton

$10000 loss

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Basic Theory
How to test Calorific Value?
Calorimeter- a device used for measuring calorific value, it includes,
oxygen bomb
a bucket
water and stirrer
temperature measuring device
ignition device
a jacket.

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Basic Theory
Q=[E(t+C)-q]/m
t: Temperature rise
C: Cooling coefficient
q: Heat of ignition wire and additive
m: Mass of standard materials
E: Heat capacity

The energy required to raise the

temperature of the calorimeter
one arbitrary unit, J/K

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Requirement
Environment for CV analysis

Test area:
Free from drafts, direct sunlight,
radiation sources.
Room temperature and
humidity controlled desirably.

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Requirement

Apparatus
Balance

Nearest to 0.0001g.
Weekly checked for accuracy
Combustion Bomb:
Not effected by combustion or products formed
to avoid introducing heat input.
Designed to completely recover all liquid
combustion products by washing inner surface.
No gas leakage.

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Withstand 20 MPa hydrostatic pressure.

Apparatus

Requirement

Calorimeter vessel:
Tarnish-resistant coating, outer surface highly polished.
A stirrer provided for mixing water. But the stirrer should
not raise calorimeter 0.01 in 10minutes mixing.
Jacket:
Inner perimeter maintained at constant
temperature0.1
Inner surface not be >10mm from sides,
top and bottom of calorimeter vessel.

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Apparatus

Requirement

Thermometer:

Platinum resistance or thermistor thermometer.

Capable of measuring to the nearest to 0.0001 .
Sample Holder:
An open crucible of platinum, quartz or base metal alloy.
Heat treat base metal crucibles for a minimum of 4 h
at 500 to ensure the crucible surface is completely
oxidized.
Ignition Fuse and Circuit:
100-mm length, 0.16-mm diameter or smaller.
Nickel-chromium alloy, cotton thread, iron wire.
6-30V alternating or direct current.

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Reagents

Requirement

Reagent water:

Distilled water
Benzoic acid:
Pellets made from benzoic acid from NIST,
or calibrated against NIST standard material
Should be traceable to a recognized certificate value
Oxygen:
Made from liquid air, >99.5% purity, free of combustible matter.
Do not use the oxygen made by the electrolytic process

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Equipment
Automatic Equipments

5E-C5500

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5E-C5508

5E-AC/PL

Equipment
Structure

Standards

5E-C5500

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ASTM D5865
ASTM D4809
ISO 1928
GB/T213
AS 1038.5

Water flow

Cover

Vessel
Balance inlet valve

Vessel inlet valve

Bucket

reservoir

Jacket
Jacket inlet valve
Chiller

Jacket inlet pump

Vessel inlet pump

Bucket drain pump

Procedure
Step 1
Step2

Step 3

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Preparation
Analysis

Calculation

- In accordance with ASTM D5865 (10 35)

Procedure
Preparation for CV analysis
Weigh the sample

Weigh 0.8-1.2g.
Nearest to 0.0001g.

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- In accordance with ASTM D5865 (10 35)

Procedure
Preparation for CV analysis
Connect Ignition fuse

Ignition fuse touches the sample, but

not touch the crucible.

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- In accordance with ASTM D5865 (10 35)

Procedure
Preparation for CV analysis
Assemble the bomb.

Add 1.0ml water to bomb before assembly.

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- In accordance with ASTM D5865 (10 35)

Procedure
Preparation for CV analysis
Charge oxygen

Flow pressure 3.0Mpa ,keep pressure

constant for oxygen charging

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- In accordance with ASTM D5865 (10 35)

Procedure
Preparation for CV analysis
Check the leakage, load the bomb

If there is evidence of gas leakage, stop the

process.

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- In accordance with ASTM D5865 (10 35)

Procedure
CV analysis
Set the program and get start analysis

Water mass deviation

0.5g of each test.

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- In accordance with ASTM D5865 (10 35)

Procedure
CV analysis
Start stirring and observe temperature change

Temperature stability
0.001/s before ignition

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- In accordance with ASTM D5865 (10 35)

Procedure
CV analysis
ignition and analysis

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Procedure
Calculation
Formula
Qvad(gross)=[ (tEe)-e1-e2-e3-e4]/m
Ee = heat capacity
t = corrected temperature rise
e1 = acid correction
e2 = fuse correction

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e3= sulfur correction

e4 = combustion aid correction
m = mass of sample

Calibration

Benzoic Acid
10 tests, RSD 0.17%

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Calibration
Overview for 5E-C5500 Automatic Calorimeter
Cal NO: 1
Bomb Vessel 1 (215)
Date Calibration: 07/02/14
Benzoic Calorific value: 26470 J/g (6,326 Kcal/kg)
Uncertainty:0.1% (K=2)
5E-C5500

NO of STD

Average
SD
%RSD

Heat
capacity(J/c)
Xi-Xbar
1
9957
2
9962
3
9960
4
9964
5
9958
6
9962
7
9966
8
9961
9
9971
10
9970
9963
4.70
0.05

(Xi-Xbar)2
-6.1
37.21
-1.1
1.21
-3.1
9.61
0.9
0.81
-5.1
26.01
-1.1
1.21
2.9
8.41
-2.1
4.41
7.9
62.41
6.9
47.61
Sum
198.90
s2
22.10
sd
4.70
%rsd
0.05

Cal NO: 1
Bomb Vessel 2 (644)
Date Calibration: 07/02/14
Benzoic Calorific value: 26470 J/g (6,326 Kcal/kg)
Uncertainty:0.1% (K=2)
5E-C5500

NO of STD

Average
SD
%RSD

Heat
capacity(J/c)
Xi-Xbar
1
9984
2
9994
3
9979
4
9977
5
9982
6
9990
7
9987
8
9987
9
9967
9982
10
9983
7.55
0.08

(Xi-Xbar)2
1
1
11
121
-4
16
-6
36
-1
1
7
49
4
16
4
16
-16
256
-1
1
Sum
513.00
s2
57.00
sd
7.55
%rsd
0.08

Cal NO: 2
Bomb Vessel 1 (215)
Date Calibration: 15/03/14
Benzoic Calorific value: 26470 J/g (6,326 Kcal/kg)
Uncertainty:0.1% (K=2)
5E-C5500

NO of STD

Average
SD
%RSD

Heat
capacity(J/c) Xi-Xbar
1
9978
2
9979
3
9989
4
9981
5
9983
6
9985
7
9981
8
9975
9
9966
10
9985
9980
6.39
0.06

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(Xi-Xbar)2
-2.2
-1.2
8.8
0.8
2.8
4.8
0.8
-5.2
-14.2
4.8
Sum
s2
sd
%rsd

NO of STD
4.84
1.44
77.44
0.64
7.84
23.04
0.64
27.04
201.64
23.04
367.60
40.84
6.39
0.06

Cal NO: 2
Bomb Vessel 2 (644)
Date Calibration: 15/03/14
Benzoic Calorific value: 26470 J/g (6,326 Kcal/kg)
Uncertainty:0.1% (K=2)
5E-C5500

NO of STD

Average
SD
%RSD

Heat
capacity(J/c) Xi-Xbar
1
9976
2
9990
3
9982
4
9984
5
9973
6
9993
7
9991
8
9981
9
9984
10
9988
9984
6.49
0.07

Remark: ASTM-D5865-10a, the precision of ten acceptable calibration test runs shall have a Relative
Standard Deviation (%RSD) no greater than 0.17%

Cal NO: 2
Bomb Vessel 1 (215)
Date Calibration: 30/04/14
Benzoic Calorific value: 26470 J/g (6,326 Kcal/kg)
Uncertainty:0.1% (K=2)
5E-C5500

Average
SD
%RSD

Heat capacity(J/c) Xi-Xbar

10013
10019
10013
10009
10004
10015
10005
10006
10002
10001
10009
6.06
0.06

(Xi-Xbar)2
4
10
4
0
-5
6
-4
-3
-7
-8
Sum
s2
sd
%rsd

16.00
100.00
16.00
0.00
25.00
36.00
16.00
9.00
49.00
64.00
331.00
36.78
6.06
0.06

Cal NO: 2
Bomb Vessel 2 (644)
Date Calibration: 29/04/14
Benzoic Calorific value: 26470 J/g (6,326 Kcal/kg)
Uncertainty:0.1% (K=2)
5E-C5500

(Xi-Xbar)2
-8
6
-2
0
-11
9
7
-3
0
4
Sum
s2
sd
%rsd

1
2
3
4
5
6
7
8
9
10

NO of STD
64.00
36.00
4.00
0.00
121.00
81.00
49.00
9.00
0.00
16.00
380.00
42.22
6.50
0.07

1
2
3
4
5
6
7
8
9
10
Average
SD
%RSD

Heat capacity(J/c) Xi-Xbar

10018
10015
10006
9998
10005
10001
10002
10013
10005
10020
10008
7.63
0.08

(Xi-Xbar)2
10
7
-2
-10
-3
-7
-6
5
-3
12
Sum
s2
sd
%rsd

100.00
49.00
4.00
100.00
9.00
49.00
36.00
25.00
9.00
144.00
525.00
58.33
7.64
0.08

Operation Notes
Release the pressure

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Operation Notes
Rinse the bomb

All parts of the bomb should be

rinsed

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Operation Notes
Check bomb before every analysis.
Do not fire the bomb if theres evidence of gas leakage.

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Operation Notes
Do not fire the bomb if its dropped
or turned over after loading.

Do not extend any portion of body

over calorimeter during ignition.

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Maintenance
Do calibration whenever significant alteration
made in the measurement system.

Do hydrostatic test for bomb,

every 5000 analysis or 2 years.
Replace the water every 3 months, and recalibrate.

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Maintenance
Valves, gauges, gaskets should meet industry safety codes.

Do not be stained with oil, grease or

combustible.

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Comparison
Main difference between ASTM, ISO, GB

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Application
Biomass or high volatile matter
For biomass, or higher volatile matter sample, wrap with lens paper.

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Oil or High CV Matter

Application

For oil or high CV matter, reduce the sample mass.

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