Fuel 90 (2011) 35933601

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Fuel
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Comparison of approaches to determine hydrogen consumption during

catalytic hydrotreating of oil fractions
L.C. Castaeda, J.A.D. Muoz, J. Ancheyta
Instituto Mexicano del Petrleo, Eje Central Lzaro Crdenas Norte 152, 07730 Mxico, DF, Mexico

a r t i c l e

i n f o

Article history:
Received 14 July 2010
Received in revised form 18 November 2010
Accepted 19 November 2010
Available online 5 February 2011
Keywords:
Hydrogen consumption
Hydrotreating
Oil fraction

a b s t r a c t
Different approaches to calculate the hydrogen consumption during hydrotreating of petroleum fractions
are reviewed and discussed. Experimental information about the hydrotreating of various distillates
(naphtha, light and heavy gasoils, atmospheric and vacuum residues) obtained in a bench-scale unit at
typical operating conditions and commercial catalysts was used to determine the hydrogen consumption
from global hydrogen balance and from the hydrogen balance in gas streams. The comparison of experimental hydrogen consumption calculated with the different approaches indicates that there is not a
method that can predict hydrogen consumption with good accuracy. For quick calculation some correlations can be used, but the error can be as high as 15%. The common approach used in reneries, which
does not take into account the dissolved hydrogen in the hydrotreated liquid, can give deviations up
to 6% with respect to the experimental value. To account for this dissolved hydrogen into the balance
all the correlations reported in the literature are suitable.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Hydrogen is perhaps one of the most important products in a
modern petroleum renery. Hydrogen is typically produced by
reforming of natural gas, but its most common source is from catalytic reforming of naphtha. Hydrotreating (HDT) and hydrocracking
(HDC) are the principal processes that consume hydrogen. Hydrogen
balance is of signicant interest and concern for reners since the
operation policy of some plants can be dictated by its availability.
For instance, if the naphtha catalytic reformer either has operational
problems or is in maintenance there is not sufcient hydrogen to
send to the HDT/HDC units which may cause shutdown of these
plants. Hydrogen is then an important utility in the production of
clean fuels such as low-sulfur gasoline and diesel.
A particular commercial HDT unit regularly operates with catalyst and feed having more or less similar properties thus the required amount of hydrogen does not vary signicantly. However,
when notorious changes in properties of catalyst and feed are
experienced the more accurate knowledge of hydrogen consumption
for these new conditions is required to anticipate possible effects
on the renery global hydrogen balance. Also when new catalyst
formulations are tested on different experimental scales, e.g.,
micro-reactor, bench-scale reactor, pilot plant, or new applications
of hydrotreating process are developed, hydrogen consumption is
Corresponding author. Fax: +52 55 9175 8429.
E-mail addresses: lcastane@imp.mx (L.C. Castaeda), jancheyt@imp.mx (J.
Ancheyta).
0016-2361/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2010.11.047

one process parameter that needs to be properly determined for

developing mass balances and further technical and economical
studies.
The common approach to calculate hydrogen consumption is by
the difference between the amount of hydrogen entering the reactor and the amount of hydrogen leaving the reactor, which is a
hydrogen balance in the gas phase. There are other approaches that
are based on simple contributions of the hydrogen consumed by
the different reactions taking place during hydrotreating, by
hydrogen balance in the liquid phase, i.e., liquid feed and liquid
product, by global hydrogen balance which involves all the streams
entering and leaving the reactor, and by chemical reaction calculations. Each of these approaches requires different physical and
chemical characterization of the liquid and gas streams as well
as other parameters which are needed for the hydrogen balance.
Depending on the precision of the experimental technique and
setup different error is introduced to the hydrogen consumption
calculation. For instance, Mapiour et al. [1] developed a multiparameter model that comprises correlations between hydrogen
partial pressure and hydrotreating conversions, using a heavy
gasoil (HGO) from Athabasca bitumen as feed. They observed that
H2 dissolution and H2 consumption increase with increasing H2
partial pressure. Lee et al. [2] reported a comparison of three ways
to calculate hydrogen consumption: by hydrogen balance in the
gas phase, by hydrogen balance in the liquid phase and by the different reactions taking place during hydrotreating. They conrmed
that using gas analyses alone to determine the H2 consumption
produced the less reliable results for pilot plant hydrodesulfurization

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L.C. Castaeda et al. / Fuel 90 (2011) 35933601

Nomenclature
Gas0
Liq0
Gas1
Liq1
(H2)0
(H2)1
H0Gas
H0Liq
H1Gas
H1Liq

DHgas
H1diss
Hcons
H1HC-Liq
HHC-Liq
H1H2 S
Hchem
HHDS

HHDN

HHDO
HHDM
HHGO
HHDA

HHDC
sg
S
Y

total amount of gas feed (kg)

total amount of liquid feed (kg)
total amount of gas product (kg)
total amount of liquid product (kg)
total amount of hydrogen entering the reactor (kg)
total amount of hydrogen leaving the reactor (kg)
total amount of hydrogen fed to the reactor (kg)
total amount of hydrogen contained in the liquid
feedstock (kg)
total amount of hydrogen in the gas reactor product (kg)
total amount of hydrogen contained in the hydrotreated
liquid product (kg)
difference between the amount of hydrogen entering
and leaving the reactor determined by mass balance in
the gas streams (kg)
amount of hydrogen dissolved in the liquid product (kg)
total real hydrogen consumption (scf/bbl)
amount of the hydrogen contained in liquid (kg)
amount of the hydrogen contained in light
hydrocarbons in liquid (kg)
amount of the hydrogen contained as H2S in gas (kg)
hydrogen consumption for consuming chemical
reactions (Nm3/m3 oil)
hydrogen consumption in hydrodesulfurization reactions (scf/bbl in Eq. (20), Nm3/m3 oil in Eqs. (8) and
(15))
hydrogen consumption in hydrodenitrogenation reactions (scf/bbl in Eq. (21), Nm3/m3 oil in Eqs. (8) and
(15))
hydrogen consumption in hydrodeoxygenation reactions
(Nm3/m3 oil)
hydrogen consumption in hydrodemetalization reactions
(scf/bbl)
hydrogen consumption in olens saturations reactions
(Nm3/m3 oil)
hydrogen consumption in aromatics saturation reactions (scf/bbl in Eq. (23), Nm3/m3 oil in Eqs. (12), (17),
and (18))
hydrogen consumption in hydrocraking reactions (scf/bbl)
specic gravity at 60 F
total sulfur content (wt.%)
liquid yield (volumetric fraction)

(HDS) with a feed comprising 62 vol.% straight-run heavy gasoil,

10 vol.% coker light gasoil, and 28 vol.% FCC light cycle oil, to
produce ultra low sulfur diesel (ULSD). Stratiev et al. [3] found
that a correct hydrogen balance in a renery may be obtained
by using chemistry of processes running at hydrogen consuming
units and those producing hydrogen such as catalytic reforming,
steam reforming, and hydrotreating of petroleum fractions. They
developed equations to provide information about the consumed
hydrogen for HDS, hydrodearomatization, hydrogenation and
hydrodenitrogenation reactions in commercial units, which allow
for optimization of renery hydrogen consumption.
Ramachandran and Menon [4] discussed a brief review on various uses of hydrogen in the industry. They pointed out that in
modern reneries hydrogen requirement is commonly about
1 wt.% of crude processed. Typical hydrogen consumption data
for various renery processes are presented in Table 1. Hydrocracking of vacuum distillates requires a large amount of hydrogen,
not only for desulfurization, but also for the increase in the hydrogen/carbon ratio of the products relative to the feed [5].

N
O
Br
MA
BT
DBT
PNA
TriA
DiA
Mw

q
qL
Hdiss
Hpurity
PH
GO
T
H
c H2

gN
k
n

e
VR
QL
CH
CT-cons
HT-cons
k

total nitrogen content (ppmw in Eq. (9), wt.% in Eq. (19))

total oxygen content (wt.%)
bromine number (gBr/100 g)
monoaromatics content (wt.%)
benzothiophene sulfur content (wt.%)
dibenzothiopene sulfur content (wt.%)
poliaromatics content (wt.%)
triaromatics content (wt.%)
diaromatics content (wt.%)
molecular weight
density at 20 C (g/mL)
liquid density (g/mL)
hydrogen solubility (scf/bbl)
hydrogen purity (wt.%)
hydrogen partial pressure (MPa)
gas/oil ratio (mL/mL)
temperature (C)
Henry coefcient
concentration of hydrogen in solubility equation
(mol H2/m3 oil)
molar gas volume at standard conditions (mol/L)
solubility coefcient ((NL H2)/(kg oil) (MPa))
catalyst remaining relative activity
catalyst bed void fraction
catalyst bed volume (m3)
oil volumetric ow rate (m3/s)
remaining hydrogen demand of oil (mol H2/m3 oil)
total hydrogen consumption (mol H2/m3 oil)
the experimentally measured hydrogen consumption
(mol H2/m3 oil)
intrinsic reaction rate constant ((m3 oil)2/[(m3cat )
(mol H2) (s)])
reaction order

Subscripts
f
feed
p
products
Superscripts
0
inlet
1
outlet

In the near future, practically all fractions of sour crudes will be

subjected to catalytic processes that involve hydrogen. The total
quantity of fractions directed to hydrotreating and hydrocracking
will amount to 90% of the total crude run [5]. It is therefore
mandatory to determine the hydrogen consumption with high
accuracy.

Table 1
Typical hydrogen consumption data for various renery processes.
Process

Wt.% on feed

Wt.% on crude

Hydrotreating
Straight run naphtha
Cracked naphtha

0.05
0.71.0

0.01
0.050.1

Hydrodesulfurization
Low sulfur gasoil to <0.05%S
High sulfur gasoil to >0.05%S

0.15
0.35

0.04
0.05

Cycle oils hydrogenation

Hydrocracking vacuum gasoil

3
23

0.3
0.50.8

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L.C. Castaeda et al. / Fuel 90 (2011) 35933601

The aim of this work is to describe and analyze the different approaches that exist to calculate the hydrogen consumption in
hydrotreating of petroleum fractions. Experimental data obtained
in bench-scale are used to test the different methods.
2. Hydrogen consumption
Hydrogen consumption during hydroprocessing is dependent
upon the feedstock properties, impurities removal, conversion level and properties of the catalyst. The heavier feed requires substantially more addition of hydrogen to attain a xed level of
upgrading [6]. Developing detailed mass balances in order to know
not only that all streams in the process are well accounted but also
the distribution of hydrogen in those streams is of vital importance
to perform further studies regarding the commercial application of
a new process and catalyst. The usual manner for calculating
hydrogen consumption is by means of experimental data either
by a hydrogen balance in gas streams or with hydrogen content
in the liquid feed and products. Fig. 1 shows all the streams involved in a general mass balance in an HDT reactor, where Gas0
and Liq0 are the total amounts of the gas stream entering the reactor, and liquid feedstock to be hydrotreated respectively. Gas1 and
Liq1 are the total amount of the gas product, which contains the
unreacted hydrogen, hydrogen sulde as by-product and light
hydrocarbons ranging from C1 to C4, and the total amount of
hydrotreated liquid product respectively.
From Fig. 1, the following mass balances can be derived:
0

Global balance : Gas0 Liq Gas1 Liq

Hydrogen balance in gas streams : H2 0 H2 1 DHgas

Global hydrogen balance : H0Gas H0Liq H1Gas H1Liq

where (H2)0 and (H2)1 are the total amounts of hydrogen entering
and leaving the reactor respectively. If the hydrogen purity is assumed to be close to 100%, Gas0 = (H2)0, DHgas is the difference between the amount of hydrogen entering and leaving the reactor
determined by mass balance in the gas streams, which is commonly
(and erroneously) reported as hydrogen consumption. H0Gas and H1Gas
are the total equivalent amounts of hydrogen contained in the gas
streams entering and leaving the reactor respectively which are

composed by pure hydrogen, hydrogen contained in H2S, and

hydrogen contained in C1C6 hydrocarbons as shown in Fig. 1. H0Liq
and H1Liq are the total amounts of hydrogen contained in the liquid
feedstock and in the hydrotreated liquid product respectively. H1Liq


includes the hydrogen content in the liquid H1HC-Liq , and the


amount of hydrogen gas dissolved in the liquid H1diss :

H1Liq H1HC-Liq H1diss

The total real hydrogen consumption (Hcons) is thus:

Hcons DHgas H1diss

H1Liq

5
H0Liq

The values of
and
are preferably obtained experimentally,
e.g., by ultimate (elemental) analysis, however, they can be estimated with empirical correlations.
Based on all these equations, which are derived from mass balances, the following approaches can be established for calculating
hydrogen consumption during hydrotreating operations.
2.1. Mass balance of hydrogen in gas stream
The most-known method for calculating hydrogen consumption
in hydrotreating units is by measuring the amount of hydrogen at
the inlet (H2)0 and at the outlet (H2)1 of the reactor system. The difference between these two amounts, according to Eq. (2), is just a
delta of hydrogen and not the chemical hydrogen consumption.
This approach, although being the most commonly used in commercial hydrotreating plants, has been reported to be not accurate
[2,5]. The application of this method requires data of ow rates of
the gas streams entering and leaving the reactor, which are frequently reported in volumetric basis as well as the gas stream
composition measured by online gas chromatography (GC).
The real H2 consumption can be then calculated by adding the
dissolved H2 in the liquid product to the delta of hydrogen (DHgas)
determined by the gas stream balance, according to Eq. (5).
2.2. Global hydrogen balance
The calculation of hydrogen consumption by measuring the
hydrogen content in the liquid feed (H0Liq ) and in the hydrotreated

Fig. 1. Streams involved in a mass balance of HDT units.

3596

L.C. Castaeda et al. / Fuel 90 (2011) 35933601

Table 2
Empirical correlations to estimate the hydrogen content in petroleum fractions.
Authors

Correlation

Riazi et al. [7,8]

%H

Observations
Weight percentages of N, O, or metals are negligible in
comparison with those of C, H, and S
Valid for: Mw = 84459 Tb = 60480 C n = 1.381.51 %H = 12.215.6 wt.%

100%S
1CH

Goossens [9]

%H 30:646

ASTM D-3343 [10]

b 7:018xA
 0:901xA
%H 5:24070:01448T
sg

82:95265:34n

306
Mw

Developed with 247 aviation fuels and 84 pure hydrocarbons

0:01298xA T b  0:01345T b 5:6879

%H = 52.825  14.260n  21.329sg
 0.0024Mw  0.052S + 0.7571n(m)
%H = 11.7  12.89sg + 0.0389AP
%H = 26  15sg
%H = 14.9  6.38xA

Dhulesia [11]
JenkinsWalsh [12]
Bureau of Standards [13,14]
Goodger [15]
Korsten and Hoffman [21]

Developed with 33 different FCC feedstocks

Developed for jet fuels with aniline points in the range of 5677 C
The oldest and simplest approach
Derived from data on jet fuels
Correlation to calculate the solubility of hydrogen in the HDT product

k a0 a1 T a2 qT a3 T 2 a4 q12

Mapiour et al. [1]

Correlation for estimating the solubility of hydrogen

Hdiss 23:95817 0:67529HPurity 3:56483P H

0:002159GO  0:003948HPurity 2 0:23328P 2H
0:11314HPurity P H 0:0001697HPurity GO

%H: hydrogen weight percent, CH: carbon-to-hydrogen weight ratio, q: liquid density at 20 C, n: refractive index at 20 C, Mw: molecular weight, Tb: average value of boiling
points calculated with 10, 50, and 90 vol.% of distilled product in Kelvin, sg: specic gravity 60 F/60 F, xA: fraction of aromatics in the mixture, AP: aniline point in K, m:
viscosity at 98.9 C in cSt, P: pressure in MPa, and GO: H2/HC ratio, HPurity: hydrogen purity.

liquid product (H1Liq ) is usually a more accurate method than that

based on gas streams as Eq. (2). The experimental determination
of hydrogen in liquid feed and product can be done by different
alternatives: ASTM D-5291 (ultimate analysis) standardized method which is regularly used to simultaneously measure total carbon,
hydrogen and nitrogen (C, H, N), ASTM D-4808 by nuclear magnetic resonance (NMR), and ASTM D-6733 by high resolution gas
chromatography.
All of these methods require the use of analytical equipment;
unfortunately, such equipments are not always available in the
reneries. Alternatively, the hydrogen content can be estimated
by the empirical correlations reported in Table 2.
In order to complete the global balance of hydrogen the total
equivalent amounts of hydrogen contained in the gas streams
entering and leaving the reactor, H0Liq and H0Liq , should be taken into
account. Therefore, hydrogen consumption (Hcons) from global
hydrogen balance is calculated as follows:

Hcons H1Liq  H0Liq H1HC-Liq H1H2 S

2.3. Class of hydrogen-consuming chemical reactions

The chemical characterization of the streams showed in Fig. 1
can provide information to determine H2 consumption in the
various reactions taking place during hydrotreating. Lee et al. [2]
reported a method based on the sum of the stoichiometric
hydrogen consumption for each class of hydrogen-consuming
chemical reaction:

Hchem HHDS HHDN HHDO HHGO HHDA

"
HHDS 0:0252sg f Sf 

Sp sg p
Yp
sg f

"

HHDN

Np sg p
0:08sg f Nf 
Yp
sg f
"

HHDO

Op sg p
0:05sg f Of 
Yp
sg f
"

HHGO 1:4sg f Brf 

Brp sg p
Yp
sg f

#
8

#
9

"

HHDA

"
#
"
##
PNAp sg p
MAp sg p
3:3sg f PNAf 
Y p 3 MAf 
Yp
sg f
sg f
12

Eqs. (8) and (9) were derived considering the following generic
reactions:

Cn Hn S mHDS H2 ! Cn Hn2x1 H2 S

13

Cn Hn N mHDN H2 ! Cn Hn2x3 NH3

14

For HDS (Eq. (13)) and HDN (Eq. (14)), mHDS and mHDN are the stoichiometric H2 consumption, i.e. the molar ratio of H2 to hydrocarbon of
the generic reactions. The authors assumed mHDS = 1 for mercaptans,
2 for suldes, 3 for disuldes, 3 for benzothiophenes, 4 for thiophenes, 2 for di-benzothiophenes and mHDS = 3.6 for a typical diesel
feedstock. While mHDN = 1 for primary amines, 2 for secondary
amines, 3 for tertiary amines, 1 for anilines, 4 for pyroles, 6 for indoles, 7 for quinolines or carbazoles, and mHDN = 5 for a typical diesel
feedstock. Similarly, for HDO, mHDO was assumed to be of 5 and for
HDA, mHDA = 3.3 (polyaromatics to monoaromatics) and mHDA = 3
(monoaromatics to cyclic saturates) [2].
Since Bromine will react with the amount of carbon doublebonds in the oil, Bromine number was used to measure olen content and it was further used to calculate H2 consumption with Eq.
(11).
Stratiev et al. [3] reported a similar method for hydrogen consumption with chemical analysis of the streams and the main reactions in an HDT process. The study was carried out using diesel and
gasoil HDT units with different feeds and operating conditions
leading to the following equations:

 

1000
Y p BTp
 Sp
HHDS 3 Sf
32
320


qf
10DBTf
Y p DBTp
22:4
 Sp
2 Sf
32
320
100


qf
1000
10Y p
22:4
 Op
HHGO Of
Mwf
Mwp
100

#
10
#
11

 

1000
10Y p
 PNAp
HHDA PNA 2 PNAf
Mwf
Mwp


qf
1000
10Y p
22:4
 MAp
3 MAf
Mwf
Mwp
100

15

16

17

L.C. Castaeda et al. / Fuel 90 (2011) 35933601

HHDADiTriA
2 
 
 
10Y
Yp
 TriAp Mwpp TriAf  TriAp 100
2 TriAf 1000
DiAf
Mw
f
6


4
10Y
3 MAf  MAp Mwpp

100
Mwf

10Y

 DiAp Mwpp

3597

 3

qf
7
522:4
100
18


HHDN 5


qf
Nf
Y p Np
22:4

140 100 140
100

19

These authors assumed that the amount of H2 consumed by HDO

reactions in HDT of diesel is negligible. It was reported that feed
quality has considerable inuence on the hydrogen chemical consumption and conrmed earlier reported studies. The difference
of experimental and calculated hydrogen consumption with these
equations was found to be 29.2%.
2.4. Hydrogen consumption by reaction average contributions
The calculation of hydrogen consumption when experimental
information is not sufcient or for quick estimations can be done
according to acquired experience. Edgar [16] reported the following average contributions of each HDT reaction to the hydrogen
consumption (scf/bbl):

HDS 95100 per each 1 wt% removed

20

HDN 300350 per each 1 wt% removed

21

HDC 25 per each 1 vol:% removed

22

HDA 27 per each 1 wt% removed

23

HDM 26 per each 1 ppm removed

24

In addition to Edgar equations, Speight [17] presented a correction

in hydrogen consumption by metal content (Table 3).
2.5. Hydrogen consumption by kinetic modeling
In general, the calculation of hydrogen consumption by means
of kinetics is done by the summation of the rates of all H2-consuming reactions, of course, the stoichiometry of each reaction, i.e. stoichiometric coefcients must be taken into account. Thus, the more
reactions the kinetic model includes in which hydrogen is present
the better and more precision in the estimation of hydrogen
consumption.
Various simplied approaches based on kinetics have been reported in the literature. Papayannakos and Georgiou [18] developed a kinetic model for hydrogen consumption during catalytic
hydrodesulfurization of a residue in a trickle-bed reactor. The
atmospheric residue of Greek petroleum deposits in the Aegean
Sea was used as feedstock. They found that the kinetic model correlated well the experimentally measured hydrogen consumption.

Table 3
Correction in hydrogen as function of metals content in petroleum fractions.
Ni + V (ppm)

Correction (%)

Ni + V (ppm)

Correction (%)

0100
200
300
400
500
600

2
1
2.5
4
6.5
9

700
800
900
1000
1100
1200

12
16
21
28
38
50

These authors established a differential mass balance equation

for hydrogen using an isothermal plug-ow reactor model. The total hydrogen consumption represents the concentration of all the
bonds likely to react with hydrogen at the reaction conditions before any treatment occurs. The observed reaction rate of hydrogen
consumption comprises the sum of the reaction rates of hydrogen
with the bonds likely to react in oil. In the absence of intraparticle
diffusion effects the following equation was derived:

 
VR
C H 1a  C T-cons 1a a  1n1  ek
QL

25

where CH is the remaining hydrogen demand or, the concentration

of the bonds which are bound to react with hydrogen at the reaction
conditions, expressed in mol H2 per m3 of the oil, CT-cons the total
hydrogen consumption, n the catalyst remaining relative activity,
e the catalyst bed void fraction, VR the catalyst bed volume, QL the
oil volumetric ow rate, k the intrinsic rate constant that includes
the hydrogen partial pressure term (k = kPH2 ) and a the reaction order which depends on the concentration and reactivity of the reacting molecules.
The reaction order and the total hydrogen consumption were
determined by regression analysis of the experimental data. The
total hydrogen reaction rate was found to be of second order,
a = 2, while the total hydrogen consumption was determined to be
257 Nm3 H2/m3 oil; within the temperature range of 350430 C
for two catalyst types. The predicted value of hydrogen consumption
from diagrams in the literature based on the API gravity of the
residue, is 207 Nm3 H2 =m3 oil [19].
Beuther and Schmid [20] measured the hydrogen consumption
during a vacuum residue HDS and found a value of 277 Nm3
H2 =m3 oil for 99.2% hydrodesulfurization. For a second-order
reaction of hydrogen consumption, Eq. (25) takes the form:

 
1
Hcons
VR
1  ek
n HT-cons  Hcons HT-cons
QL

26

The authors reported a graphical correlation of the experimental

data for the calculation of the intrinsic reaction rate constant k
in the temperature range of 350430 C, and another correlation
of Arrhenius plot of the intrinsic rate constants for hydrogen
consumption.

3. Solubility of hydrogen
To properly determine the hydrogen consumption in the hydrogen mass balance, the solubility of the hydrogen in the liquid
streams on Fig. 1 is required. The mass-balance equations are
based on the assumption that the gasliquid equilibrium can be
described by Henrys law as follows:

gN
kqL

27

where H is the Henry coefcient, gN the molar gas volume at standard conditions, k the solubility coefcient and qL the density of the
liquid under process conditions. The concentration of hydrogen
cH2 can be then estimated by the following equation:

3598

cH2

L.C. Castaeda et al. / Fuel 90 (2011) 35933601

qH2

28

Korsten and Hoffman [21] reported the following correlation to calculate the solubility of hydrogen in the HDT product:

k a0 a1 T a2

a3 T 2 a4

q2

29

where a0 = 0.559729; a1 = 0.42947  103; a2 = 3.07539  103;

a3 = 1.94593  106; a4 = 0.835783, T is the temperature in C, q
the density at 20 C in g/cm3, and k the hydrogen solubility coefcient given in (NL H2)/[(kg oil) (MPa)].
Riazi and Roomi [22] proposed a method for predicting the solubility of hydrogen in petroleum fractions at different conditions of
temperature and pressure. The proposed method is applicable to
fractions with molecular weight ranging from 70 to 650 which is
equivalent to carbon number ranging from 6 to 46.
Riazi and Vera [23] proposed a parafnic/naphthenic/aromatic
compositional model for calculating the solubility of light gases
such as methane, ethane, carbon dioxide, and hydrogen in various
petroleum and coal liquid fractions under different conditions of
temperature and pressure. The proposed method derived correlations where the solubility of a gas in a liquid mixture, in terms of
its mole fraction, can be calculated from the vaporliquid
equilibrium.
Mapiour et al. [1] also developed the following correlation for
estimating the solubility of hydrogen (Hdiss):

low pressure separator is the hydrotreated product whose ow is

quantied in the owmeter.
Table 4 shows the operating conditions for the different experiments conducted at bench-scale. Some feedstocks were prepared
by blending various streams as indicated in the table. Table 5 describes the catalysts used in the experiments. Table 6 reports the
characterization of the feed and product for each hydrotreating
test. Global mass balances for all experiments (Eq. (1)) showed relative error lower than 0.8%, while the global hydrogen balances
(Eq. (3)) presented relative error lower than 1%. Therefore, the
experimental data obtained from the HDT of petroleum fractions
can be reliable used to determine the hydrogen consumption.
All the existent methods for hydrogen consumption calculations in HDT of petroleum fractions, including kinetics models,
were described in the previous section. Since some models require
thermodynamic properties, kinetic parameters, as well as catalysts
properties, and because this information is currently unavailable,
they were not included in the following discussion.
4.2. Global hydrogen balance
The global hydrogen balance was performed according to the
ultimate analysis of liquid streams and gas chromatography as
illustrated in Fig. 1. Hydrogen contained in gas compounds such
as H2S and light hydrocarbons was calculated from molar equivalents, assuming that all is present only in the gas product (Gas1).
This global hydrogen balance was considered to determine the

Hdiss 23:95817 0:67529HPurity 3:56483PH

0:002159GO  0:003948HPurity 2 0:23328P2H
0:11314HPurity PH 0:0001697HPurity GO

30

where PH is the H2 partial pressure in MPa, (HPurity) is hydrogen

purity at the entrance of the reactor in wt.%, and GO is the
hydrogen-to-oil ratio in mL/mL.
The amount of hydrogen gas dissolved in the liquid can also be
calculated from experimental data by using the AspenHysys simulator and the vapor liquid equilibrium at typical operating conditions in the storage container of hydrotreated liquid product. The
Chao Seader equation of state (EOS), which is reported as valid
for temperatures below 257 C [1], can be applied to perform equilibrium calculations.

Table 4
Operating conditions in bench-scale experiments.
Feedstock

Condition

Naphtha hydrodesulfurization
(HDSN)

Naphtha

P: 54.8
T: 290
LHSV: 5
H2/HC: 664

Gasoil
Hydrodesulfurization (HDSD)

Gasoil
Kerosene
Light gasoil from HDSG

P: 54
T: 360
LHSV: 2.4
H2/HC: 2200

Heavy gasoil
Hydrodesulfurization (HDSG)

Coker gasoil
Light cycle oil (LCO)

P: 139
T: 338
H2/HC: 2000
LHSV: 6 (HDM)
LHSV: 0.78 (HDS)

Hydrotreating of atmospheric
residue (HDAR)

Atmospheric residue

P: 100
T: 397
H2/HC: 5000
LHSV: 0.25

Hydrocracking of vacuum
residue (HDVR)

Vacuum residue
LCO
Lube oil extract

P: 175
T: 410
H2/HC: 3200
LHSV: 0.18

4. Results and discussion

4.1. Experimental data
Different data collected from previous experiments in a benchscale unit for hydrotreating of naphtha (HDSN), gasoil for diesel
(HDSD), heavy gasoil (HDSG), atmospheric (HDAR) and vacuum
(HDVR) residua were used to test the various approaches to determine hydrogen consumption.
The bench-scale unit comprises two streams as feedstock:
hydrogen and hydrocarbon. Both streams are quantied and controlled by mass owmeters. Hydrogen is directly fed from a high
pressure cylinder using a high pressure regulator to control the inlet gas pressure. Pressure of liquid feed is controlled by a pump.
Temperature of the feed entering the reactor is controlled by an
electric heating system.
The reactor is of xed-bed type. The reaction product is a liquidvapor mixture that is sent to a high pressure separator, the
liquid stream leaving this separator is sent to a low pressure separator where the separation of the remaining vapor components of
the liquid occurs. The gases produced in the low pressure and high
pressure separators are analyzed in a gas chromatograph and mass
ow is measured by the owmeter. The liquid product from the

P: pressure in kg/cm2, T: temperature in C, LHSV: liquid hourly space velocity in

h1, H2/HC: hydrogen hydrocarbon ratio in ft3std/bbl.

Table 5
Catalysts used for bench-scale experiments.
Catalyst type Application

Size (inches)

CoMo
NiMo
CoMo
CoMo
NiMo

1/8
1/8
1/20
1/14
1/32

Naphtha hydrodesulfurization (HDSN)

Gasoil hydrodesulfurization (HDSG)
Heavy gasoil hydrodesulfurization (HDS HGO)
Hydrotreating of atmospheric residue (HDT AR)
Hydrocracking of vacuum residue (HDCVR)

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L.C. Castaeda et al. / Fuel 90 (2011) 35933601

Table 6
Properties of feed and product of hydrotreating experiments.
Properties

HDSN

Ultimate analysis
Carbon
Hydrogen
Specic gravity 60/60 F
Density 20/4 C
Refractive index
Molecular weight
Average boiling point
Viscosity @ 99 C
Bromine number

HDSG

HDS HGO

HDT AR

HDV VR

Units

Feed

Product

Feed

Product

Feed

Product

Feed

Product

Feed

Product

wt.%
wt.%

84.95
14.86
0.7303
0.7268
1.4064
104
105.8
0.3539
1.87

84.37
15.55
0.7288
0.7253
1.4055
102.3
103.1
0.33
0.01

85.37
13.31
0.8774
0.8745
1.4895
225.3
275.3
1.195
3.81

85.22
14.14
0.8625
0.8596
1.4806
220.8
270.4
1.153
1.17

85.43
11.6
0.929
0.9261
1.5196
278.4
320.7
2.202

85.27
12.89
0.8882
0.8853
1.4947
258.7
301.5
1.83

81.00
13.23
1.0232
1.0203
1.5456
602.6
563.1
1315

86.19
15.93
0.9428
0.9399
1.5146
443.4
450.8
164

82.16
13.57
1.0199
1.017
1.5413
625.4
576.1
1560.71

81.82
16.26
0.929
0.9261
1.5212
277.2
302.9
3.126

g/mL
g/gmol
C
cSt
gBr/100 g
wt.%

0.1911
0.1204
0.0707

0.0085
0
0.0085

1.126
1.0608
0.0652

0.0055
0
0.0055

2.868
2.5812
0.2868

0.405
0.162
0.243

5.52

0.8725

4.268

1.029

Total aromatics
Poliaromatics
Monoaromatics
Asphaltenes
Total nitrogen
Olens
Nickel
Vanadium

vol.%

10.230
4.23
6.0

1.4
0.889

8.540
3.54
5.0

0.3
0.715

41.5
12.0
29.5

246
2.6

31.2
11.7
19.5

0.3
2.4

53.2
13.4
39.8

1504
3.1

48.5
10.0
29.5

447
2.8

20.57
3200

104
501

6.3
1500

46
152

14.15
4400

77.21
412.19

6.2
2210

14.2
13.82

wt.%
ppm
vol.%
ppm
ppm

Experimental hydrogen consumption,

ft3std/bbl

experimental hydrogen consumption which is represented by Eq.

(6).
Fig. 2 shows the hydrogen consumption calculated from experimental data for the different feedstocks. With the global hydrogen
balance it is conrmed that hydrogen consumption depends on the
nature of the feed. This already known behavior is because heavy
fractions contain higher concentration of impurities such as sulfur,
nitrogen, asphaltenes, aromatics and metals, and their removal requires higher amounts of hydrogen. The different values of hydrogen consumption are also due to the type of reaction occurring
during the HDT of each feedstock. Hydrotreating of light and middle fractions mainly comprises HDS reaction. Although other reactions, (hydrodenitrogenation, hydrodearomatization and olens
saturation) occur in less extent, while for heavy fractions hydrodemetalization and hydrocracking also take place.
The global hydrogen balance requires experimental ultimate
analyses to determine hydrogen consumption that is why it is
rarely reported by reneries, and they prefer the use of a quick approach as that given by Eq. (2). Alternatively, the correlations reported in Table 2 can be applied to calculate hydrogen content in
liquid streams.
Fig. 3 shows a comparison of the experimental hydrogen consumption and that determined from the global hydrogen balance
using correlations to calculate the hydrogen content in liquid
streams.

1400
1200
1000
800

Hydrogen consumption, ft3std/bbl

Total sulfur
Benzothiophenes
Di-benzothiophenes

Experimental
Dhulesia
Goossens
Bureau of standards

HDSN

HDSD

Riazi-Daubert
Jenkins-Walsh
ASTM D-3343
Goodger

HDSG

HDAR

HDVR

Fig. 3. Hydrogen consumption by global hydrogen balance with correlations for

hydrogen content in liquid streams.

Some correlations exhibited better performance for heavy feeds

while others did for light feeds, which is due to the range of application in which they were developed. In general, the use of correlations to determine the hydrogen content of liquid streams to
further calculate the global hydrogen balance tends to underestimate the hydrogen consumption as compared with the experimental value. For HDS of light distillates the correlations yield quite
similar hydrogen consumption with the lowest error respect to
the experimental one. The highest errors are found for HDS of heavy feeds.
The correlations to calculate hydrogen content from only one liquid property (Bureau of Standards and Goodger) result to be the
worst for predicting hydrogen consumption. ASTM D-3343 correlation also exhibited large error, probably due to its application to
light and pure hydrocarbons.
The best correlations to be used for hydrogen content calculations were the following:

600

For HDS of naphtha: JenkinsWalsh

For HDS light and heavy gasoils: Dhulesia
For HDT of AR and VR: Goosens

400
200
0
0

10

20

30

40

50

60

70

Feedstock API gravity

Fig. 2. Hydrogen consumption by global hydrogen balance with experimental data.

All of them presented deviation from experimental hydrogen

consumption in the range of 915%. This behavior corresponds
more or less to the range of application reported by the authors.

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L.C. Castaeda et al. / Fuel 90 (2011) 35933601

4.3. Hydrogen balance in gas streams

4.4. Class of hydrogen-consuming chemical reactions

Hydrogen consumption, ft3 std/bbl

Correlations of Lee and StratievTzingov were used to estimate

the hydrogen consumption from the properties of liquid streams
entering and leaving the reactor. These correlations, which are similar and dependent on feedstock and product properties, were
developed for HDT of light gasoils.
Hydrogen consumption calculated from these correlations was
compared with that obtained from the experimental global hydrogen balance. The results are shown in Fig. 5. Hydrogen consumption for HDS of AR and VR is not presented because these
correlations do not include contributions of the HDM and hydrocracking reactions. In general, it is observed that the correlations

Experimental
Mapiour-Sundaramurty

HDSN

HDSD

Korsten-Hoffman
Hysys

HDSG

HDAR

HDVR

Fig. 4. Hydrogen consumption by hydrogen balance in gas stream with correlations

for dissolved hydrogen.

Experimental

700

Lee

Stratiev-Tzingov

600
500
400
300
200
100
0
HDSN

HDSD

HDSG

Fig. 5. Hydrogen consumption by chemical reactions.

1400

Hydrogen consumption,
ft3 std/bbl

The hydrogen balance in gas streams was performed with

the amount of hydrogen entering and leaving the reactor as well
as the amounts of hydrogen dissolved in the liquid, hydrogen
contained in H2S, and hydrogen contained in C1C6 hydrocarbons determined experimentally by GC and molar equivalents
calculations.
The amount of dissolved hydrogen for all fractions was relatively low because the conditions at storage container of HDT liquid product are close to ambient and the solubility of hydrogen
is strongly dependent of pressure and temperature. The value of
hydrogen dissolved in the hydrotreated liquid stream was not obtained experimentally, but only by using two different correlations,
the detailed calculation was not considered appropriate to be included in this manuscript.
Fig. 4 shows for all the hydrotreated fractions the hydrogen consumption obtained from hydrogen balance in gas streams, the dissolved hydrogen from correlations and calculations using Hysys
simulator.
The dissolved hydrogen from KorstenHoffman and Mapiour
Sundaramurthy correlations and that determined by Hysys led to
similar results. Hydrogen consumption determined from Eq. (5)
showed deviations lower than 0.23% respect to the global hydrogen
balance on the HDT of light and heavy gasoils, while the observed
error in the HDT of heavy fractions was between 1.14% and 2.73%.
In general, hydrogen consumption calculated from the hydrogen
balance in gas streams is close to that obtained by the global
hydrogen balance.
The dissolved hydrogen accounts for 0.16% of total hydrogen
consumption from hydrogen balance in gas streams as expressed
by Eq. (2). This certainly not a high contribution, is the most likely
reason why reners use the difference between the amount of
hydrogen entering and leaving the reactor in the gas streams,
DHgas, to report the hydrogen consumption.

Hydrogen consumption, ft3std/bbl

800

Experimental

1200

Edgar-Speight

1000
800
600
400
200
0
HDSN

HDSD

HDSG

HDAR

HDVR

Fig. 6. Hydrogen consumption by reactions average contribution.

underpredicted the hydrogen consumption and they have the lowest error for HDS of light gasoil, which is in agreement with their
range of application.
4.5. Hydrogen consumption by reaction average contributions
EdgarSpeight approach was developed to calculate the hydrogen consumption in HDT as function of feedstock and product
properties.
Fig. 6 presents the hydrogen consumption estimated by using
EdgarSpeight method and its comparison with the experimental
value from the global hydrogen balance. The predictions are clearly
better for HDT of heavy feed. The error for HDS of light petroleum
fractions is higher than 50%.
5. Conclusions
The accurate hydrogen consumption cannot be directly measured from operational data of hydrotreating units. The common
manner to calculate hydrogen consumption by using the amount
of hydrogen in the gas entering and leaving the reactor can underestimate it in about 6%. Hydrogen balance, which includes ow
rate data, GC analysis, liquid analysis and dissolved hydrogen calculations is required to determine the real H2 consumption.
The best correlations to be used for hydrogen content calculations in liquid streams were the following: JenkinsWalsh correlation for naphtha, Dhulesia correlation for light and heavy gasoils,
and Goosens correlation for AR and VR.
The dissolved hydrogen obtained from KorstenHoffman,
MapiourSundaramurthy and Hysys calculations was similar; hence,
the use of any of these approaches is suitable.
For quick calculation the correlations of Lee and Stratiev
Tzingov can be used to estimate hydrogen consumption by
chemical reactions contributions for HDT middle fractions, while
the approach developed by Edgar and Speight is better for heavy
fractions.

L.C. Castaeda et al. / Fuel 90 (2011) 35933601

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