Transcript Detailed Hydrocarbon Analyser (DHA)

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PRODUCTS for PETROCHEMISTRY
•
Detailed Hydrocarbon Analysis
of the primary petrol, refinery compounds
and final products
В
2500
2000
1500
1000
500
0
0
20
40
60
мин
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PRODUCTS for PETROCHEMISTRY
Precise purity determination for
benzene, toluene, xylene and
another petrochemical products
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PRODUCTS for PETROCHEMISTRY
Quality Control for primary petroleum
processing installations, catalytic
reforming installations and
other processing objects
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PRODUCTS for PETROCHEMISTRY
Refinery Gas Analysis,
Water and Sulphur determination in
petroleum products
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PRODUCTS for PETROCHEMISTRY
And also other standard and
custom analytical measurements
using UNICHROM
system
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PRODUCTS for PETROCHEMISTRY
Simple implementation of analytical
measurements according to GOST,
ASTM and other certificate
documentation in
automatic mode!
And also
The Detailed Hydrocarbon Analysis
of
AUTOMOTIVE PETROLS
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PRODUCTS for PETROCHEMISTRY
• Detailed Hydrocarbon Analysis is
made using
Automotive Petrol Analyser
The gas chromatograph equipped with
Flame-ionisation detector which has
detection limit less than 210-12 gC/s
and oven programming capability from
35 to 300 C with rate 5 C/min
+ UNICHROM-DHA
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PRODUCTS for PETROCHEMISTRY
The most important parts of
Automotive Petrol Analyser
The gas chromatographic capillary column
with stationary liquid phase of
polymdimethylsyloxane, length 50 meters,
diameter 0.32 mm and film thickness
0,52 m
+
Capillary column connection interface with
capability of splitting carrier flow into rate
1 : 100 and detector makeup gas
10
20
30
В
0
20
40
22 мин
32
0
ми н 5 0
80
В
300 identified components
60
40
and the same quantity of unknowns
34
20
200 0
500
3 6.0
100 0
0
36
мин
3 6.5
3 7.0
C11 (3) из оп ар афи н ?
1 00
C10 (1 ) а ро мат ик а ?
мин10
C1 0 (1 )а ро мат ик а ?
18
1 -мет ил -2-н -пр оп ил бе нзо л
н-б ут ил бе нзо л
1 ,3-д име ти л-5 -эт ил бе нзо л
1 -мет ил -4-н -пр оп ил бе нзо л
2 2.0
1,2 -ди эт ил бе нзо л
16
2 1.5
?
300 0
8
2 1.0
1 -мет ил -3-н -пр оп ил бе нзо л
2 0.5
1,3 -ди эт ил бе нзо л
20
?
1000
?
2000
с сс -1,2 ,3 -тр име ти лц ик ло пе нт ан
цис -2-бут ен
3-э ти лге кс ан
н-о кт ан
тр ан с-1 ,2-д име ти лц икл оге кс ан
ци с-1 -мет ил -3-э ти лц ик ло пе нт ан
тр ан с-1 -мет ил -2-э ти лц ик ло пе нт ан
тр ан с-1 ,3-д име ти лц икл оге кс ан
40
н-б ут ил ци кл оге кса н
6
30
?
В
1-мет ил -2-и зо пр оп ил бе нзо л
4
мин
1 -мет ил -1-э ти лц ик ло пе нт ан
50
тр ан с-1 -мет ил -3-э ти лц ик ло пе нт ан
В
?
?
3.8
1 ,1-д име ти лц икл оге кс ан
20
2,2 ,4 -тр име ти лге кс ан
3000
?
3.6
В
?
В
400 0
3.4
60
?
3.2
т ранс -2-бут ен
2,2-димет илпропан
30
тр ан с-1 ,4-д име ти лц икл оге кс ан
10
н-бут ан
2-мет илпропан
пропан
50 В
1-бут ен
эт ан
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PRODUCTS for PETROCHEMISTRY
40
And as result
мин
1000
500
0
ми н
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PRODUCTS for PETROCHEMISTRY
Software module of UNICHROM system
«DHA.DLL» is automatically
identifies known and unknown
components
Using of special algorithms for
interpolation of physical and chemical
substance properties to unknown
components allows to complement our
knowledge about petroleum sample being
analysed
9
8
7
6
5
4
3
2
1
0
0
-1
1
2
3
4
5
6
7
8
9
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PRODUCTS for PETROCHEMISTRY
We made calculations using internal
normalisation method taking in
account detector response factors
В
0.00020
0.00015
0.00010
В
3.5
мин
4.0
В
0.00020
В
0.004
0.00015
0.003
0.002
0.0010
0.00010
0.001
25
26
27
мин
28
В
0.000
4
6
8
10
мин
0.0005
So we have got
В
VOLUME, MASS and MOLAR content of
0.0015
15
20
мин
25
0.000085
ALL individual hydrocarbons
0.000080
В
0.00014
0.0010
45
0.00012
0.00010
0.00008
35
40
0.0005
0
10
20
30
40
50
мин
45
мин
46
47
48
49
мин
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PRODUCTS for PETROCHEMISTRY
Relative error of concentration
determination
LESS THAN
± 3.6 %
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PRODUCTS for PETROCHEMISTRY
Using components content
the UNICHROM DHA module calculates the
following parameters of lead-free
automotive petrol
•Fractional contents
•Saturated vapour pressure
•Motor octane number
•Research octane number
•Density
The automatic gas
chromatographic system for
detailed determination of petrol
components and the basic petrol
parameters
В
0.0015
0.0010
0.0005
0
10
20
30
40
50
мин
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The automatic gas chromatographic system
UNICHROM for the detailed hydrocarbon analysis
(DHA) of various petroleum fractions and products
has been developed.
Samples of gasoline are analysed by
temperature programmed gas chromatograph on a
high-resolution capillary column which separates
hydrocarbons in order of their boiling points.
Individual components are identified
comparing their Kovats or linear retention indices
with a library of 330 components.
Then all the major gasoline standardised
specifications are calculated from the obtained DHA
data.
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As the result of single chromatographic petrol sample analysis (about 70
min) it is possible to determine such characteristics:
- Detailed hydrocarbon and fractions contents (conforms ASTM D5134,
GOST 6994 and ASTM D5580, GOST 8997 and GOST 2070),
- Contents of aromatic components (conforms GOST 6994 and ASTM
5580),
- Contents of olefin components (conforms GOST 8997 and 2070),
- Fractional content (conforms GOST 2177 and ASTM D86),
- Detonation stability expressed in terms of research octane number
RON (conforms GOST 8226 and ASTM 2699),
- Detonation stability expressed in terms of motor octane number MON
(conforms GOST 511 and ASTM 2700),
- Saturated vapour pressure (conforms GOST 1756-52 and ASTM 2889),
- Density (conforms GOST 3900 and ASTM 4052).
The high reproducibility and the reliability of developed system
UNICHROM in the Central Laboratory of the Mozyr Oil Refinery (Belarus)
and in The State Criminal Centre of the Home Office of Belarus has been
achieved. The method is certified at The State Metrology Committee of
Belarus (No. MVI.MN 998-99).
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Petroleum analysis report No 18
File: C\Unichrom\DB - Petroleum Products\Column HP-1 19091Z-115\Petroleum.$$$
Spectrum name: PETROLEUM ( DATE: 21.10.98. TIME: 15:43 )
Chromatogram name: Fuel Station-IV, Minsk: Novopolotzk Oil Refinery Plant; RON 82.0 MON 77.0
Detailed Analysis (322 peaks processed)
No
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Component name
Ethane
Propane
2-methylpropane
1-butene
n-butane
trans-2-butene
2.2-dimethylpropane
cis-2-butene
3-methyl-1-butene
Cyclobutane
2-methylbutene
1-pentene
2-methyl-1-butene
n-pentane
trans-2-pentene
cis-2-pentene
t'
0.05
0.16
0.32
0.41
0.46
0.51
0.53
0.59
0.81
0.85
0.96
1.11
1.18
1.24
1.33
1.44


I lin
200.00
300.00
354.19
385.20
400.00
406.52
409.19
416.56
445.19
450.11
464.74
483.76
493.27
500.00
504.60
509.72
I log
200.00
300.00
366.44
390.40
400.00
410.60
414.63
425.01
457.43
462.07
474.76
489.15
495.65
500.00
507.51
515.29
% vol
% mass
0.023
0.017
0.340
0.266
0.776
0.584
0.020
0.016
3.297
2.599
0.012
0.010
0.024
0.020
0.013
0.011
0.008
0.006
0.000
0.000
7.571
6.381
0.018
0.016
0.033
0.029
8.027
6.834
0.040
0.036
0.018
0.016
% mol
0.054
0.562
0.937
0.027
4.173
0.017
0.025
0.018
0.009
0.000
8.253
0.021
0.039
8.839
0.047
0.022


320 n-pentadecane
321 1-hexadecene
322 n-hexadecane
Total:
48.26
50.64
50.88
g/l
0.130
1.969
4.325
0.118
19.265
0.075
0.146
0.079
0.048
0.002
47.296
0.115
0.216
50.652
0.263
0.122
mol/l
0.004
0.045
0.074
0.002
0.331
0.001
0.002
0.001
0.001
0.000
0.656
0.002
0.003
0.702
0.004
0.002
0.049
0.040
0.065
741.178
0.000
0.000
0.000
7.943


1500.00
1590.71
1600.00
1500.00
1590.93
1600.00
0.006
0.005
0.008
100.000
0.007
0.005
0.009
100.000
0.003
0.002
0.004
100.000
Fractional analysis
Group name
Paraffins
Isoparaffins
Aromatics
Naphthenes
Alkenes
Oxidants
Other
% vol
24.190
32.484
32.548
9.253
0.992
0.003
0.530
Quality parameters
Substance quantity, mol/l:
Oxygen content, % mass:
Hydrogen content, % mass:
Density, g/l:
Motor octane number:
Research octane number:
Saturated vapor pressure (on fractional analysis data):
Saturated vapor pressure (on detailed analysis data):
Fractional analysis on GOST 2177A
distill. %
distill. T, °C
% mass
21.227
29.333
38.412
9.570
0.931
0.003
0.524
% mol
24.734
30.100
34.363
9.504
0.963
0.004
0.332
7.94
7.16E-04
1.35E+01
741.18
77.10
82.38
59.949 kPa
62.602 kPa
IBR
10%
50%
40.19 59.11
100.26
g/l
157.333
217.411
284.700
70.933
6.897
0.024
3.880
mol/l
1.965
2.391
2.729
0.755
0.076
0.000
0.026
Here is petroleum
analysis report
with detailed
hydrocarbon
analysis data and
distillation curve
was generated
using DHA data.
(449.66 mm Hg)
(469.56 mm Hg)
90%
FBR
155.96
190.46
Fractional content
250
T d is till, °С
200
150
100
50
0
0
10
20
30
40
50
60
70
80
90
100
distillation percentage, % vol
Figure 1. Petroleum analysis report. Fractional content of gasoline calculated from DHA data.
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Intensity, nA
The typical chromatogram of gasoline
2500
2000
1500
1000
500
0
0
10
20
30
Fig. 1. The typical chromatogram of gasoline.
40
50
Time. min
мин
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Density values calculated from GC analysis, g/L
800
790
780
y = 1,0037x
R2 = 0,9943
770
760
750
740
730
720
710
710
720
730
740
750
760
770
780
790
Density values measured by the standardized method in accordance with ASTM 4052
and GOST 3900, g/L
800
Comparison of D (Density) values calculated from GC analysis and measured
by the standardised method in accordance with ASTM 4052 and GOST 3900
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FC values calculated from GC analysis, °С
225
200
175
y = 1,0058x
R2 = 0,9985
150
125
100
75
50
25
25
50
75
100
125
150
175
200
225
FC values measured by the standardized method in accordance with ASTM D86 and
GOST 2177, °С
Comparison of FC (Fractional Content) values calculated from GC
analysis and measured by the standardised method in accordance
with ASTM D86 and GOST 2177
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90
88
MON calculated from GC analysis
86
y = 1,0007x
R2 = 0,9868
84
82
80
78
76
74
74
76
78
80
82
84
86
88
90
MON values measured by the standardized engine method in accordance with ASTM
D2700 and GOST 511
Comparison of MON (Motor Octane Number) values calculated from
GC analysis and measured by the standardised engine method in
accordance with ASTM D2700 and GOST 511.
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102
RON calculated from GC analysis
100
98
96
y = 1,0033x
R2 = 0,9895
94
92
90
88
86
84
82
80
78
78
80
82
84
86
88
90
92
94
96
98
100
102
RON values measured by the standardized engine method in accordance with
ASTM D2699 and GOST 8226
Comparison of RON (Research Octane Number) values calculated
from GC analysis and measured by the standardised engine
method in accordance with ASTM D2699 and GOST 8226
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SVP values calculated from GC analysis, кПа
90
y = 1,0146x
R2 = 0,8601
80
70
60
50
40
30
20
20
30
40
50
60
70
80
SVP values measured by the standardized method in accordance with ASTM 2889 and
GOST 1756, kPa
Comparison of SVP (Saturated Vapour Pressure) values calculated
from GC analysis and measured by the standardised method in
accordance with ASTM 2889 and GOST 1756
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250
of distillation,
Temperature
Температура
отгона, °С °C
225
200
175
150
125
100
75
50
25
0
0
10
20
30
40
50
60
70
80
90
100
Процент
отгона, об.%
Distillation
%
FC (Fractional Content) diagram of gasoline calculated from DHA data.
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No
group
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Chromatographic group
Components eluted before n-butane
n-Butane
Components eluted between n-butane and 2methylbutane
2-methylbutane
Components eluted between 2-methylbutane and
n-pentane
n-Pentane
Components eluted between n-pentane и 2methylpentane
2- and 3-methylpentane and components eluting
between them
Components eluted between 3-methylpentane
and n-hexane
n-Hexane
Components eluted between n-hexane and
benzene
Benzene
Components eluted between benzene and 2methylhexane
2 and 3-Methylhexane and components eluting
between them
Components eluted between 3-methylhexane
and n-heptane
М,
a.u.м.
47
48
47
SVP,
kPa
496100
348500
286900
MON
RON
102,57
88,9
80,34
125,44
113,12
215,66
72
70
141500
123300
89,78
115,08
96,25
180,32
72
76
107800
67800
59,71
110,37
30,85
122,76
86
44600
74,6
108,9
82
36300
77,28
104,4
86
92
34300
30600
38,23
58,26
19,46
124,14
78
95
22300
19300
87,33
41,48
111,94
43,47
100
16600
89,5
55,74
96
14600
91,53
90,36
The individual and border compounds of 31 chromatographic groups.
Group 1 to 15.
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16 n-Heptane
17 Components eluted between n-heptane and
toluene
18 Toluene
19 Components eluted between toluene and 2methylheptane
20 2 and 3-Methylheptane and components eluting
between them
21 Components eluted between 3-methylheptane
and n-octane
22 n-Octane
23 Components eluted between n-octane and
ethylbenzene
24 Ethylbenzene
25 Components eluted between ethylbenzene and
m-xylene
26 m-Xylene and p-xylene
27 Components eluted between p-xylene and oxylene
28 o-Xylene
29 Components eluted after up to and including nnonane
30 Components eluted between n-nonane and ndecane
31 n-Decane and components eluted after n-decane
100
94
11200
10600
34,38
49,56
15,04
34,38
92
114
7200
5300
93,85
70,07
126,28
188,36
114
4800
36,83
16,15
113
4000
48,48
25,18
114
126
3600
2700
45,59
49,22
32,85
39,55
106
127
2500
2400
84,27
36,57
248,76
14,8
106
127
2300
2000
109,87
33,39
62,54
19,95
106
130
1800
1300
120,04
34,49
58,62
16,1
134
900
82,23
138,58
141
400
98,65
48,49
The individual and border compounds of 31 chromatographic groups.
Group 16 to 31.
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