CHAPTER

05

MATERIAL BALANCE
CALCULATIONS

1
Material & Energy balance

Following are the material and energy balance calculations based on the properties we
calculated earlier. The Procedure we adopted is based on the outline given in book
G.H James Petroleum Refining- Technology & Economics. As we stated earlier that we
used API Technical Databook for properties estimation, Enthalpy values are also from the
graphs given in that book.

Basis:
25000 Barrels per day (BPD) Atmospheric Gas Oil
1800 standard cubic ft per barrel Hydrogen
(at 673 to 700 K & 100 bar reactor operating conditions)

Initial data required:

Watson characterization factor Kw An index of feedstock quality and

correlating data based on physical properties (12.5 for paraffinic stocks to 10 for
highly aromatics)
MeABP ( OR )
3
Kw
sp gravity (60 / 60O F )

where T10 T50 T90

MeABP
3
API gravity An arbitrary scale expressing the gravity or density of liquid
petroleum products (less than 0 for heavy oils to 340 for CH4)

141.5
o
API 131.5
sp gr (60 / 60o F )

Preliminary steps:

1. Yield estimation
2. Kw and API gravity of products
3. Severity determination

Yield estimation can either be made from graphs for yield estimation or from refinery
data or we can select yield analysis from Refinery Handbooks. So we selected Yield
analysis against our feed HGO (Heavy Gas Oil) from Hydroprocessing Journal as it was
easily available. Following are the graphs which are necessary for Preliminary Material
Balance Calculations before detail calculatios across each equipment

2
Material & Energy balance

Graph for estimation of vol % yield of C5 180 oF

Figure 1

3
Material & Energy balance

Graph for estimation of vol % yield of 180 o-400oF

Figure 2

4
Material & Energy balance

Graph for estimation of Kw of Feed and Product

Figure 3

5
Material & Energy balance

Graph for estimation of H2 wt% by weight in feed and product

Figure 4

Reactions chemistry is very important in material balance calculations. Following is the

total chemistry of our hydrocracking system

6
Material & Energy balance

H2 S H2S H S H2S
2

N 2 3H 2 2 NH
N 3H 2 NH
NH 3H S NH HS
2

3
2

2
3

NH 3 H 2 S NH 4 HS

Inside hydrotreating reactor

Inside hydrotreating reactor

After water addition

NH4HS dissolves in water and exit as sour water

7
Material & Energy balance

Feedstock : Atm gas oil

Basis = 25000 BPD
1041.66667 bbl / hr
Severity = 1800 scf / bbl (first basis based
on data for HGO in Journal
Feed Analysis :
vol % = 100
API = 32.2
sp-gr = 0.86
S%= 1.37
N2 % = 0.031
C residue % = 0.07
(ramsbottom ):
Kw (by using formula of
VABP) 11.90
Feed = 12.61
Gasoline= 12.16
Naphtha=

TOTAL BALANCE
Compon vo BPD API (lb/h lb / wt lb/h wt lb lb / K
ent l r) / hr % rS % / hr C w
% BPD S N2 h resid
fact r ue
or N
2

Feed
HGO 100 25000 32.2 12.61 315250 1.37 4319 0.031 98 220.7 11.9
H2 (scf/bbl) 1800 9938
Total 325188
Product
H2S (wt%)
NH3 (wt%)
C (wt%)
C3 4 1000 147.2 7.42 7424
i-C4 8.2 2050 119.8 8.23 16879
n-C4 5.4 1350 110.6 8.55 11538
Gasoline 41.3 10325 79 9.83 101487
Naphtha 66.6 16650 56.8 10.99 182952
CH4 & 0.5 1634
C2H6 (wt%)
Total 31375 326841

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Material & Energy balance

HYDROGEN BALANCE
H2 out
Component wt % (from lb / hr (S & lb / hr H2
graph) N2 free)
H2S (wt%) 5.9 270
NH3 (wt%) 17.65 21
C (wt%)
C3 18.2 7424 1351
i-C4 17.2 16879 2910
n-C4 17.2 11538 1989
Gasoline 16 101487 16238
Naphtha 14.5 182952 26528
CH4 & C2H6 (wt%) 21.7 1634 355
Assume H2 Loss in solution (1 1042
lb/bbl feed)
Total 326841 50413
H2 in
HGO 11.9 310833 36989
Hydrogen 100 9938 9938
Total 46927
Actual Severity Requirement
H2 added to complete deficiency 3486
Total 50413

Added H2 = 15785660 scf /day = 631.426 scf /bbl feed

Total severity = 2431 scf/bbl feed

Now again calculating total feed and H2 in

Compon vo BPD API (lb/h lb / wt lb/h wt lb lb / K

ent l r) / hr % rS % / hr C w
% BPD S N2 h resid
fact r ue
or N
2

Feed
HGO 100 25000 32.2 12.61 315250 1.37 4319 0.031 98 220.7 11.9
H2 (scf/bbl) 2431 13421
Total 328671

Component wt % (from lb / hr (S & lb / hr H2

graph) N2 free)
H2 in
HGO 11.9 310833 36989
Hydrogen 100 13421 13421
Total 50410

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Material & Energy balance

Results
: lb/hr kg/hr
H2 consumed for
Hydrocracking = 13421 6093
H2 for S & N2 = 291 132
H2 dissolved in porducts = 1042 473

Total non-recycled H2 = 14754 6698

Now, Hydrogen is balanced. In stream 36, total 6226 kg/h H2 is going percentage going
in R-101 is 42.03% which amounts to 2617 kg/h, and in stage 2, 57.97% is going which
amounts to 3609 kg/h. Overall picture based on above calculations would be as follows

Total Feed in H Total yield out

HGO 143124 Kg/h Y C3 3370 Kg/h
D Kg/h
H2 6093 Kg/h
R
i-C4 7663
Total 149217 Kg/h O n-C4 5238 Kg/h
(S) 1961 Kg/h C Gasoline 46075 Kg/h
(N2) 44 Kg/h R Kg/h
A Naphtha 83060
(C) 100 Kg/h Kg/h
C C1, C2 742
K H2S 2083 Kg/h
I
NH3 54 Kg/h
H2 Elemental Balance (In) N
G C 100 Kg/h
H2 in
Total 148386 Kg/h
hydrocarbon feed 16793 Kg/h
U
(S & N free) N
H2 as severity I
(for 6093 Kg/h T H2 Elemental Balance (Out)
hydrocracking) H2 out in
H2 for S and N2 132 Kg/h converted 22415 Kg/h
Total 23018 Kg/h hydrocarbons
H2 loss in
473 Kg/h
solution
H2 in ammonia &
132 Kg/h
Hyd. Sulfide
Total 23020 Kg/h

Note balance across two reactors is based on recycled amounts of hydrogen and feed and
% conversion selected (40 % in first reactor R-101 & 60 % in second reactor R-102,
across separators is based on flash calculations and across distillation column is based on
bubble point and dew point calculations. So final results may vary slightly from
preliminary calculations above. Also in refinery projects it is hard to eliminate the
difference in calculations because of complex nature of petroleum fractions and more

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Material & Energy balance

volume % of product than feed (which is 124 % in our case). We calculated Recycled
amount of hydrogen based on iterations on excel. Excel sheet is in CD with this project.
distil

Material balance calculations equipment wise are as follows. Note that we used API
Technical Databook for enthalpy calculations Chapter 7

HYDROCRACKER R-101

Conversion 40 % INLET OUTLET

Stream # 5 43 6
Components kg/hr kg/hr kg/hr
Atm. oil 143124 - 85874
H2 3462 7601 8682
H2S - - 2083
NH3 - - 54
C1,C2 - - 297
C3 - - 1348
n-C4 - - 2095
i-C4 - - 3065
Gasoline - - 18430
Naphtha - - 33224
C residue - - 100
Total 146586 7601 155253
Grand Total 154187 155253

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Material & Energy balance

Enthalpy (kJ/kg) 1.851E+08 4.145E+07 2.717E+08

T (K) 673 358 688
P (kPa) 9990 10130 9890
HYDROCRACKER R-102

Conversion 60 % INLET OUTLET

Stream # 21 48 22
Components kg/hr kg/hr kg/hr
Atm. oil 85874 - 85874
H2 4331 6497 7455
H2S - - -
NH3 - - -
C1,C2 - - 445
C3 - - 2022
n-C4 - - 3143
i-C4 - - 4598
Gasoline - - 27645
Naphtha - - 49836
C residue - -
Total 90205 7601 95144
Grand Total 154187 155253
Enthalpy (kJ/kg) 1.41.E+08 3.871E+07 1.830 E+08
T (K) 700 420 730

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Material & Energy balance

P (kPa) 9990 10130 9890

13
Material & Energy balance

HP SEPERATOR HS-101

INLET OUTLET
Stream # 9 10 40 52
Components kg/hr kg/hr kg/hr kg/hr
Atm. oil 85874 85874 - -
H2S 2083 - 1976 -
NH3 54 - - -
H2 8682 236 8578 -
C1,C2 297 297 - -
C3 1348 1348 - -
n-C4 2095 2095 - -
i-C4 3065 3065 - -
Gasoline 18430 18430 - -
Naphtha 33224 33224 - -
C residue 100 100 - -
NH4HS - - - 162
Water 7156 - - 7156
Total 162409 144669 10553 7318
Grand total 162409 162412
Enthalpy (kJ/kg) 8.61947E 3.9 E+07 4.497.E+ 2.964E+
+07 07 06
T (K) 343 343 343 343
P (kPa) 9750 1720 8000 690

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Material & Energy balance

HP SEPERATOR HS-102

46

24

25

INLET OUTLET
Stream # 24 25 46
Components kg/hr kg/hr kg/hr
Atm. oil - - -
H2S - - -
NH3 - - -
H2 7455 236 7219
C1,C2 445 445 -
C3 2022 2022 -
n-C4 3143 3143 -
i-C4 4598 4598 -
Gasoline 27645 27645 -
Naphtha 49836 49836 -
C residue - - -
NH4HS - - -
Water - - -
Total 95144 87926 7219
Grand total 95144 95145
Enthalpy (kJ/kg) 7.98E+07 3.649E+07
T (K) 410 420 410
P (kPa) 9750 1750 9750

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Material & Energy balance

LP SEPERATOR LS-101

INLET OUTLET (by flash

calculations on API
tech. data book.)
Stream # 11 12 13 53
Components kg/hr kg/hr kg/hr kg/hr
Atm. oil 85874 85874 85874 -
H2 473 473 6 468
C1,C2 742 742 158 584
C3 3370 3370 1939 1431
n-C4 5238 5238 4299 939
i-C4 7663 7663 5871 1795
Gasoline 46075 46075 46075 -
Naphtha 83060 83060 83060 -
C residue 100 100 100 -
Total 232596 232596 227382 5217
Grand Total 232596 232596 232599
Enthalpy (kJ/kg) 7.549E+07 6.434.E+07 6.204E+07 -
T (K) 388 308 308 305
P (kPa) 1735 273 273 265

Following are the results of Flash calculations done in API Technical Data book.

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Material & Energy balance

Note:

Pseu000 is gasoline
Pseu001 is Naphtha
Pseu002 is HGO

Material Balance for distillation column is in the chapter of DESIGN OF DISTILATION

COLUMN because it requires detailed calculations of bubble point and dew point which
in turn decides the temperature and pressure conditions throughout the column.

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Material & Energy balance

Simulation in HYSYS

For simulation of HYDRORAKING UNITS and other Refinery units, special

applications of HYSYS and ASPEN PLUS are used because of involvement of hundreds
of reactions and complex chemistry of petroleum fractions.

To simulate Hydrocracking unit in HYSYS, an integrated version named HYSYS REF

SYS is used, and to simulate it in ASPEN PLUS, an excel based version is available in
package of ASPEN software named ASPEN RXREFINERY. Remember, to obtain correct
and real time results, there is a need of specialization in these special versions, which can
only be obtained by repeated practice and full knowledge of petroleum chemistry.

We simulated our HYDROCRACKING UNIT in HYSYS REF SYS but to converge the
unit is difficult because it needs repeated calibrations. The results can be seen in CD with
this project. Just the view of simulation is presented here.

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Material & Energy balance

The simulation of hydrocracking pla

19