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 a b s t r a c t

Article history: Different approaches to calculate the hydrogen consumption during hydrotreating of petroleum fractions
Received 14 July 2010 are reviewed and discussed. Experimental information about the hydrotreating of various distillates
Received in revised form 18 November 2010 (naphtha, light and heavy gasoils, atmospheric and vacuum residues) obtained in a bench-scale unit at
Accepted 19 November 2010
typical operating conditions and commercial catalysts was used to determine the hydrogen consumption
Available online 5 February 2011
from global hydrogen balance and from the hydrogen balance in gas streams. The comparison of exper-
imental hydrogen consumption calculated with the different approaches indicates that there is not a
Keywords:
method that can predict hydrogen consumption with good accuracy. For quick calculation some correla-
Hydrogen consumption
Hydrotreating
tions can be used, but the error can be as high as 15%. The common approach used in reneries, which
Oil fraction 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 one process parameter that needs to be properly determined for

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 cata-
lytic 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 cata-
lyst and feed having more or less similar properties thus the re-
quired 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).
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 reac-
tor 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 calcula-
tions. 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 multi-
parameter 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 dif-
ferent 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

0016-2361/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2010.11.047
3594 L.C. Castaeda et al. / Fuel 90 (2011) 35933601

Nomenclature

Gas0 total amount of gas feed (kg) N total nitrogen content (ppmw in Eq. (9), wt.% in Eq. (19))
Liq0 total amount of liquid feed (kg) O total oxygen content (wt.%)
Gas1 total amount of gas product (kg) Br bromine number (gBr/100 g)
Liq1 total amount of liquid product (kg) MA monoaromatics content (wt.%)
(H2)0 total amount of hydrogen entering the reactor (kg) BT benzothiophene sulfur content (wt.%)
(H2)1 total amount of hydrogen leaving the reactor (kg) DBT dibenzothiopene sulfur content (wt.%)
H0Gas total amount of hydrogen fed to the reactor (kg) PNA poliaromatics content (wt.%)
H0Liq total amount of hydrogen contained in the liquid TriA triaromatics content (wt.%)
feedstock (kg) DiA diaromatics content (wt.%)
H1Gas total amount of hydrogen in the gas reactor product (kg) Mw molecular weight
H1Liq total amount of hydrogen contained in the hydrotreated q density at 20 C (g/mL)
liquid product (kg) qL liquid density (g/mL)
DHgas difference between the amount of hydrogen entering Hdiss hydrogen solubility (scf/bbl)
and leaving the reactor determined by mass balance in Hpurity hydrogen purity (wt.%)
the gas streams (kg) PH hydrogen partial pressure (MPa)
H1diss amount of hydrogen dissolved in the liquid product (kg) GO gas/oil ratio (mL/mL)
Hcons total real hydrogen consumption (scf/bbl) T temperature (C)
H1HC-Liq amount of the hydrogen contained in liquid (kg) H Henry coefcient
HHC-Liq amount of the hydrogen contained in light c H2 concentration of hydrogen in solubility equation
hydrocarbons in liquid (kg) (mol H2/m3 oil)
H1H2 S amount of the hydrogen contained as H2S in gas (kg) gN molar gas volume at standard conditions (mol/L)
Hchem hydrogen consumption for consuming chemical k solubility coefcient ((NL H2)/(kg oil) (MPa))
reactions (Nm3/m3 oil) n catalyst remaining relative activity
HHDS hydrogen consumption in hydrodesulfurization reac- e catalyst bed void fraction
tions (scf/bbl in Eq. (20), Nm3/m3 oil in Eqs. (8) and VR catalyst bed volume (m3)
(15)) QL oil volumetric ow rate (m3/s)
HHDN hydrogen consumption in hydrodenitrogenation reac- CH remaining hydrogen demand of oil (mol H2/m3 oil)
tions (scf/bbl in Eq. (21), Nm3/m3 oil in Eqs. (8) and CT-cons total hydrogen consumption (mol H2/m3 oil)
(15)) HT-cons the experimentally measured hydrogen consumption
HHDO hydrogen consumption in hydrodeoxygenation reactions (mol H2/m3 oil)
(Nm3/m3 oil) k intrinsic reaction rate constant ((m3 oil)2/[(m3cat )
HHDM hydrogen consumption in hydrodemetalization reactions (mol H2) (s)])
(scf/bbl) a reaction order
HHGO hydrogen consumption in olens saturations reactions
(Nm3/m3 oil) Subscripts
HHDA hydrogen consumption in aromatics saturation reac- f feed
tions (scf/bbl in Eq. (23), Nm3/m3 oil in Eqs. (12), (17), p products
and (18))
HHDC hydrogen consumption in hydrocraking reactions (scf/bbl) Superscripts
sg specic gravity at 60 F 0 inlet
S total sulfur content (wt.%) 1 outlet
Y liquid yield (volumetric fraction)

(HDS) with a feed comprising 62 vol.% straight-run heavy gasoil, In the near future, practically all fractions of sour crudes will be
10 vol.% coker light gasoil, and 28 vol.% FCC light cycle oil, to subjected to catalytic processes that involve hydrogen. The total
produce ultra low sulfur diesel (ULSD). Stratiev et al. [3] found quantity of fractions directed to hydrotreating and hydrocracking
that a correct hydrogen balance in a renery may be obtained will amount to 90% of the total crude run [5]. It is therefore
by using chemistry of processes running at hydrogen consuming mandatory to determine the hydrogen consumption with high
units and those producing hydrogen such as catalytic reforming, accuracy.
steam reforming, and hydrotreating of petroleum fractions. They
developed equations to provide information about the consumed
Table 1
hydrogen for HDS, hydrodearomatization, hydrogenation and
Typical hydrogen consumption data for various renery processes.
hydrodenitrogenation reactions in commercial units, which allow
for optimization of renery hydrogen consumption. Process Wt.% on feed Wt.% on crude
Ramachandran and Menon [4] discussed a brief review on var- Hydrotreating
ious uses of hydrogen in the industry. They pointed out that in Straight run naphtha 0.05 0.01
Cracked naphtha 0.71.0 0.050.1
modern reneries hydrogen requirement is commonly about
1 wt.% of crude processed. Typical hydrogen consumption data Hydrodesulfurization
Low sulfur gasoil to <0.05%S 0.15 0.04
for various renery processes are presented in Table 1. Hydro-
High sulfur gasoil to >0.05%S 0.35 0.05
cracking of vacuum distillates requires a large amount of hydrogen,
Cycle oils hydrogenation 3 0.3
not only for desulfurization, but also for the increase in the hydro-
Hydrocracking vacuum gasoil 23 0.50.8
gen/carbon ratio of the products relative to the feed [5].
 L.C. Castaeda et al. / Fuel 90 (2011) 35933601
The aim of this work is to describe and analyze the different ap-
proaches 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 le-
vel and properties of the catalyst. The heavier feed requires sub-
stantially 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 in-
volved in a general mass balance in an HDT reactor, where Gas0
and Liq0 are the total amounts of the gas stream entering the reac-
tor, 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 1
Global balance : Gas0 Liq Gas1 Liq 1 This approach, although being the most commonly used in com-
Hydrogen balance in gas streams : H2 0 H2 1 DHgas 2 [2,5]. The application of this method requires data of ow rates of
Global hydrogen balance : H0Gas H0Liq H1Gas H1Liq 3 quently reported in volumetric basis as well as the gas stream
where (H2)0 and (H2)1 are the total amounts of hydrogen entering
and leaving the reactor respectively. If the hydrogen purity is as-
sumed to be close to 100%, Gas0 = (H2)0, DHgas is the difference be-
tween 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
Fig. 1. Streams involved in a mass balance of HDT units.
3595
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 4
The total real hydrogen consumption (Hcons) is thus:
Hcons DHgas H1diss 5
The values of H1Liq
and H0Liq
are preferably obtained experimentally,
e.g., by ultimate (elemental) analysis, however, they can be esti-
mated with empirical correlations.
Based on all these equations, which are derived from mass bal-
ances, 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 dif-
ference between these two amounts, according to Eq. (2), is just a
delta of hydrogen and not the chemical hydrogen consumption.
mercial hydrotreating plants, has been reported to be not accurate
the gas streams entering and leaving the reactor, which are fre-
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
3596 L.C. Castaeda et al. / Fuel 90 (2011) 35933601

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

Authors Correlation Observations

Riazi et al. [7,8] %H 100%S
1CH
Weight percentages of N, O, or metals are negligible in
comparison with those of C, H, and S
Goossens [9] %H 30:646 82:95265:34n
q  306
Mw
Valid for: Mw = 84459 Tb = 60480 C n = 1.381.51 %H = 12.215.6 wt.%
ASTM D-3343 [10] %H 5:24070:01448T b 7:018xA
 0:901xA Developed with 247 aviation fuels and 84 pure hydrocarbons
sg
0:01298xA T b  0:01345T b 5:6879
Dhulesia [11] %H = 52.825  14.260n  21.329sg Developed with 33 different FCC feedstocks
 0.0024Mw  0.052S + 0.7571n(m)
JenkinsWalsh [12] %H = 11.7  12.89sg + 0.0389AP Developed for jet fuels with aniline points in the range of 5677 C
Bureau of Standards [13,14] %H = 26  15sg The oldest and simplest approach
Goodger [15] %H = 14.9  6.38xA Derived from data on jet fuels
Korsten and Hoffman [21] k a0 a1 T a2 qT a3 T 2 a4 q12 Correlation to calculate the solubility of hydrogen in the HDT product
Mapiour et al. [1] Hdiss 23:95817 0:67529HPurity 3:56483P H Correlation for estimating the solubility of hydrogen
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 PNAp sg p MAp sg p
based on gas streams as Eq. (2). The experimental determination HHDA 3:3sg f PNAf  Y p 3 MAf  Yp
sg f sg f
of hydrogen in liquid feed and product can be done by different
alternatives: ASTM D-5291 (ultimate analysis) standardized meth- 12
od which is regularly used to simultaneously measure total carbon, Eqs. (8) and (9) were derived considering the following generic
hydrogen and nitrogen (C, H, N), ASTM D-4808 by nuclear mag- reactions:
netic resonance (NMR), and ASTM D-6733 by high resolution gas
chromatography. Cn Hn S mHDS H2 ! Cn Hn2x1 H2 S 13
All of these methods require the use of analytical equipment;
unfortunately, such equipments are not always available in the Cn Hn N mHDN H2 ! Cn Hn2x3 NH3 14
reneries. Alternatively, the hydrogen content can be estimated For HDS (Eq. (13)) and HDN (Eq. (14)), mHDS and mHDN are the stoichi-
by the empirical correlations reported in Table 2. ometric H2 consumption, i.e. the molar ratio of H2 to hydrocarbon of
In order to complete the global balance of hydrogen the total the generic reactions. The authors assumed mHDS = 1 for mercaptans,
equivalent amounts of hydrogen contained in the gas streams 2 for suldes, 3 for disuldes, 3 for benzothiophenes, 4 for thio-
entering and leaving the reactor, H0Liq and H0Liq , should be taken into phenes, 2 for di-benzothiophenes and mHDS = 3.6 for a typical diesel
account. Therefore, hydrogen consumption (Hcons) from global feedstock. While mHDN = 1 for primary amines, 2 for secondary
hydrogen balance is calculated as follows: amines, 3 for tertiary amines, 1 for anilines, 4 for pyroles, 6 for in-
Hcons H1Liq  H0Liq H1HC-Liq H1H2 S 6 doles, 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
2.3. Class of hydrogen-consuming chemical reactions (monoaromatics to cyclic saturates) [2].
Since Bromine will react with the amount of carbon double-
The chemical characterization of the streams showed in Fig. 1 bonds in the oil, Bromine number was used to measure olen con-
can provide information to determine H2 consumption in the tent and it was further used to calculate H2 consumption with Eq.
various reactions taking place during hydrotreating. Lee et al. [2] (11).
reported a method based on the sum of the stoichiometric Stratiev et al. [3] reported a similar method for hydrogen con-
hydrogen consumption for each class of hydrogen-consuming sumption with chemical analysis of the streams and the main reac-
chemical reaction: tions in an HDT process. The study was carried out using diesel and
gasoil HDT units with different feeds and operating conditions
Hchem HHDS HHDN HHDO HHGO HHDA 7
leading to the following equations:
" #
Sp sg p   
HHDS 0:0252sg f Sf  Yp 8 1000 Y p BTp
sg f HHDS 3 Sf  Sp
32 320
 
" # 10DBTf Y p DBTp qf
Np sg p 2 Sf  Sp 22:4 15
32 320 100
HHDN 0:08sg f Nf  Yp 9
sg f  
1000 10Y p qf
" # HHGO Of  Op 22:4 16
Op sg p Mwf Mwp 100
HHDO 0:05sg f Of  Yp 10
sg f   
1000 10Y p
HHDA PNA 2 PNAf  PNAp
" # Mwf Mwp
Brp sg p  
HHGO 1:4sg f Brf  Yp 11 1000 10Y p qf
sg f 3 MAf  MAp 22:4 17
Mwf Mwp 100
 L.C. Castaeda et al. / Fuel 90 (2011) 35933601 3597

HHDADiTriA
2       3
10Y Yp 10Y
2 TriAf 1000  TriAp Mwpp TriAf  TriAp 100 DiAf 100
 DiAp Mwpp qf
6 Mw f Mwf 7
4   522:4
10Y
3 MAf  MAp Mwpp 100

18

 
Nf Y p Np qf These authors established a differential mass balance equation
HHDN 5  22:4 19
140 100 140 100 for hydrogen using an isothermal plug-ow reactor model. The to-
tal hydrogen consumption represents the concentration of all the
These authors assumed that the amount of H2 consumed by HDO bonds likely to react with hydrogen at the reaction conditions be-
reactions in HDT of diesel is negligible. It was reported that feed fore any treatment occurs. The observed reaction rate of hydrogen
quality has considerable inuence on the hydrogen chemical con- consumption comprises the sum of the reaction rates of hydrogen
sumption and conrmed earlier reported studies. The difference with the bonds likely to react in oil. In the absence of intraparticle
of experimental and calculated hydrogen consumption with these diffusion effects the following equation was derived:
equations was found to be 29.2%.
 
VR
2.4. Hydrogen consumption by reaction average contributions C H 1a  C T-cons 1a a  1n1  ek 25
QL

The calculation of hydrogen consumption when experimental where CH is the remaining hydrogen demand or, the concentration
information is not sufcient or for quick estimations can be done of the bonds which are bound to react with hydrogen at the reaction
according to acquired experience. Edgar [16] reported the follow- conditions, expressed in mol H2 per m3 of the oil, CT-cons the total
ing average contributions of each HDT reaction to the hydrogen hydrogen consumption, n the catalyst remaining relative activity,
consumption (scf/bbl): e the catalyst bed void fraction, VR the catalyst bed volume, QL the
HDS 95100 per each 1 wt% removed 20 oil volumetric ow rate, k the intrinsic rate constant that includes
the hydrogen partial pressure term (k = kPH2 ) and a the reaction or-
HDN 300350 per each 1 wt% removed 21 der which depends on the concentration and reactivity of the react-
ing molecules.
HDC 25 per each 1 vol:% removed 22 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,
HDA 27 per each 1 wt% removed 23
a = 2, while the total hydrogen consumption was determined to be
257 Nm3 H2/m3 oil; within the temperature range of 350430 C
HDM 26 per each 1 ppm removed 24
for two catalyst types. The predicted value of hydrogen consumption
In addition to Edgar equations, Speight [17] presented a correction from diagrams in the literature based on the API gravity of the
in hydrogen consumption by metal content (Table 3). residue, is 207 Nm3 H2 =m3 oil [19].
Beuther and Schmid [20] measured the hydrogen consumption
2.5. Hydrogen consumption by kinetic modeling during a vacuum residue HDS and found a value of 277 Nm3
H2 =m3 oil for 99.2% hydrodesulfurization. For a second-order
In general, the calculation of hydrogen consumption by means reaction of hydrogen consumption, Eq. (25) takes the form:
 
of kinetics is done by the summation of the rates of all H2-consum- 1 Hcons VR
ing reactions, of course, the stoichiometry of each reaction, i.e. stoi- 1  ek 26
n HT-cons  Hcons HT-cons QL
chiometric coefcients must be taken into account. Thus, the more
reactions the kinetic model includes in which hydrogen is present The authors reported a graphical correlation of the experimental
the better and more precision in the estimation of hydrogen data for the calculation of the intrinsic reaction rate constant k
consumption. in the temperature range of 350430 C, and another correlation
Various simplied approaches based on kinetics have been re- of Arrhenius plot of the intrinsic rate constants for hydrogen
ported in the literature. Papayannakos and Georgiou [18] devel- consumption.
oped 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 3. Solubility of hydrogen
Sea was used as feedstock. They found that the kinetic model cor-
related well the experimentally measured hydrogen consumption. To properly determine the hydrogen consumption in the hydro-
gen mass balance, the solubility of the hydrogen in the liquid
streams on Fig. 1 is required. The mass-balance equations are
Table 3 based on the assumption that the gasliquid equilibrium can be
Correction in hydrogen as function of metals content in petroleum fractions.
described by Henrys law as follows:
Ni + V (ppm) Correction (%) Ni + V (ppm) Correction (%) gN
H 27
0100 2 700 12 kqL
200 1 800 16
300 2.5 900 21 where H is the Henry coefcient, gN the molar gas volume at stan-
400 4 1000 28 dard conditions, k the solubility coefcient and qL the density of the
500 6.5 1100 38
liquid under process conditions. The concentration of hydrogen
600 9 1200 50
cH2 can be then estimated by the following equation:
3598 L.C. Castaeda et al. / Fuel 90 (2011) 35933601

qH2 low pressure separator is the hydrotreated product whose ow is

cH2 28
H quantied in the owmeter.
Korsten and Hoffman [21] reported the following correlation to cal- Table 4 shows the operating conditions for the different exper-
culate the solubility of hydrogen in the HDT product: iments conducted at bench-scale. Some feedstocks were prepared
by blending various streams as indicated in the table. Table 5 de-
T 1 scribes the catalysts used in the experiments. Table 6 reports the
k a0 a1 T a2 a3 T 2 a4 29
q q2 characterization of the feed and product for each hydrotreating
test. Global mass balances for all experiments (Eq. (1)) showed rel-
where a0 = 0.559729; a1 = 0.42947  103; a2 = 3.07539  103;
ative error lower than 0.8%, while the global hydrogen balances
a3 = 1.94593  106; a4 = 0.835783, T is the temperature in C, q
(Eq. (3)) presented relative error lower than 1%. Therefore, the
the density at 20 C in g/cm3, and k the hydrogen solubility coef-
experimental data obtained from the HDT of petroleum fractions
cient given in (NL H2)/[(kg oil) (MPa)].
can be reliable used to determine the hydrogen consumption.
Riazi and Roomi [22] proposed a method for predicting the sol-
All the existent methods for hydrogen consumption calcula-
ubility of hydrogen in petroleum fractions at different conditions of
tions in HDT of petroleum fractions, including kinetics models,
temperature and pressure. The proposed method is applicable to
were described in the previous section. Since some models require
fractions with molecular weight ranging from 70 to 650 which is
thermodynamic properties, kinetic parameters, as well as catalysts
equivalent to carbon number ranging from 6 to 46.
properties, and because this information is currently unavailable,
Riazi and Vera [23] proposed a parafnic/naphthenic/aromatic
they were not included in the following discussion.
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 4.2. Global hydrogen balance
temperature and pressure. The proposed method derived correla-
tions where the solubility of a gas in a liquid mixture, in terms of The global hydrogen balance was performed according to the
its mole fraction, can be calculated from the vaporliquid ultimate analysis of liquid streams and gas chromatography as
equilibrium. illustrated in Fig. 1. Hydrogen contained in gas compounds such
Mapiour et al. [1] also developed the following correlation for as H2S and light hydrocarbons was calculated from molar equiva-
estimating the solubility of hydrogen (Hdiss): lents, 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
Table 4
0:11314HPurity PH 0:0001697HPurity GO 30
Operating conditions in bench-scale experiments.

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

purity at the entrance of the reactor in wt.%, and GO is the Naphtha hydrodesulfurization Naphtha P: 54.8
hydrogen-to-oil ratio in mL/mL. (HDSN) T: 290
The amount of hydrogen gas dissolved in the liquid can also be LHSV: 5
calculated from experimental data by using the AspenHysys sim- H2/HC: 664
ulator and the vapor liquid equilibrium at typical operating condi- Gasoil Gasoil P: 54
tions in the storage container of hydrotreated liquid product. The Hydrodesulfurization (HDSD) Kerosene T: 360
Light gasoil from HDSG LHSV: 2.4
Chao Seader equation of state (EOS), which is reported as valid
H2/HC: 2200
for temperatures below 257 C [1], can be applied to perform equi-
Heavy gasoil Coker gasoil P: 139
librium calculations.
Hydrodesulfurization (HDSG) Light cycle oil (LCO) T: 338
H2/HC: 2000
4. Results and discussion LHSV: 6 (HDM)
LHSV: 0.78 (HDS)

4.1. Experimental data Hydrotreating of atmospheric Atmospheric residue P: 100

residue (HDAR) T: 397
H2/HC: 5000
Different data collected from previous experiments in a bench- LHSV: 0.25
scale unit for hydrotreating of naphtha (HDSN), gasoil for diesel Hydrocracking of vacuum Vacuum residue P: 175
(HDSD), heavy gasoil (HDSG), atmospheric (HDAR) and vacuum residue (HDVR) LCO T: 410
(HDVR) residua were used to test the various approaches to deter- Lube oil extract H2/HC: 3200
mine hydrogen consumption. LHSV: 0.18
The bench-scale unit comprises two streams as feedstock: P: pressure in kg/cm2, T: temperature in C, LHSV: liquid hourly space velocity in
hydrogen and hydrocarbon. Both streams are quantied and con- h1, H2/HC: hydrogen hydrocarbon ratio in ft3std/bbl.
trolled by mass owmeters. Hydrogen is directly fed from a high
pressure cylinder using a high pressure regulator to control the in-
let gas pressure. Pressure of liquid feed is controlled by a pump.
Temperature of the feed entering the reactor is controlled by an
Table 5
electric heating system.
Catalysts used for bench-scale experiments.
The reactor is of xed-bed type. The reaction product is a li-
quidvapor mixture that is sent to a high pressure separator, the Catalyst type Application Size (inches)
liquid stream leaving this separator is sent to a low pressure sepa- CoMo Naphtha hydrodesulfurization (HDSN) 1/8
rator where the separation of the remaining vapor components of NiMo Gasoil hydrodesulfurization (HDSG) 1/8
CoMo Heavy gasoil hydrodesulfurization (HDS HGO) 1/20
the liquid occurs. The gases produced in the low pressure and high
CoMo Hydrotreating of atmospheric residue (HDT AR) 1/14
pressure separators are analyzed in a gas chromatograph and mass NiMo Hydrocracking of vacuum residue (HDCVR) 1/32
ow is measured by the owmeter. The liquid product from the
 L.C. Castaeda et al. / Fuel 90 (2011) 35933601 3599

Table 6
Properties of feed and product of hydrotreating experiments.

Properties HDSN HDSG HDS HGO HDT AR HDV VR

Units Feed Product Feed Product Feed Product Feed Product Feed Product
Ultimate analysis
Carbon wt.% 84.95 84.37 85.37 85.22 85.43 85.27 81.00 86.19 82.16 81.82
Hydrogen wt.% 14.86 15.55 13.31 14.14 11.6 12.89 13.23 15.93 13.57 16.26
Specic gravity 60/60 F 0.7303 0.7288 0.8774 0.8625 0.929 0.8882 1.0232 0.9428 1.0199 0.929
Density 20/4 C g/mL 0.7268 0.7253 0.8745 0.8596 0.9261 0.8853 1.0203 0.9399 1.017 0.9261
Refractive index 1.4064 1.4055 1.4895 1.4806 1.5196 1.4947 1.5456 1.5146 1.5413 1.5212
Molecular weight g/gmol 104 102.3 225.3 220.8 278.4 258.7 602.6 443.4 625.4 277.2
Average boiling point C 105.8 103.1 275.3 270.4 320.7 301.5 563.1 450.8 576.1 302.9
Viscosity @ 99 C cSt 0.3539 0.33 1.195 1.153 2.202 1.83 1315 164 1560.71 3.126
Bromine number gBr/100 g 1.87 0.01 3.81 1.17
Total sulfur wt.% 0.1911 0.0085 1.126 0.0055 2.868 0.405 5.52 0.8725 4.268 1.029
Benzothiophenes 0.1204 0 1.0608 0 2.5812 0.162
Di-benzothiophenes 0.0707 0.0085 0.0652 0.0055 0.2868 0.243
Total aromatics vol.% 10.230 8.540 41.5 31.2 53.2 48.5
Poliaromatics 4.23 3.54 12.0 11.7 13.4 10.0
Monoaromatics 6.0 5.0 29.5 19.5 39.8 29.5
Asphaltenes wt.% 20.57 6.3 14.15 6.2
Total nitrogen ppm 1.4 0.3 246 0.3 1504 447 3200 1500 4400 2210
Olens vol.% 0.889 0.715 2.6 2.4 3.1 2.8
Nickel ppm 104 46 77.21 14.2
Vanadium ppm 501 152 412.19 13.82

experimental hydrogen consumption which is represented by Eq.

Hydrogen consumption, ft3std/bbl

(6).
Fig. 2 shows the hydrogen consumption calculated from exper- Experimental Riazi-Daubert
Dhulesia Jenkins-Walsh
imental data for the different feedstocks. With the global hydrogen Goossens ASTM D-3343
balance it is conrmed that hydrogen consumption depends on the Bureau of standards Goodger
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 re-
quires higher amounts of hydrogen. The different values of hydro-
gen consumption are also due to the type of reaction occurring
during the HDT of each feedstock. Hydrotreating of light and mid-
dle fractions mainly comprises HDS reaction. Although other reac- HDSN HDSD HDSG HDAR HDVR

tions, (hydrodenitrogenation, hydrodearomatization and olens
saturation) occur in less extent, while for heavy fractions hydro-
demetalization 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 ap-
proach as that given by Eq. (2). Alternatively, the correlations re-
ported in Table 2 can be applied to calculate hydrogen content in
liquid streams.
Fig. 3 shows a comparison of the experimental hydrogen con-
sumption and that determined from the global hydrogen balance
using correlations to calculate the hydrogen content in liquid
streams.
Experimental hydrogen consumption,
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 appli-
cation in which they were developed. In general, the use of corre-
lations to determine the hydrogen content of liquid streams to
further calculate the global hydrogen balance tends to underesti-
mate the hydrogen consumption as compared with the experimen-
tal 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 hea-
vy feeds.
The correlations to calculate hydrogen content from only one li-

1400 quid property (Bureau of Standards and Goodger) result to be the

1200
worst for predicting hydrogen consumption. ASTM D-3343 correla-
tion also exhibited large error, probably due to its application to
1000 light and pure hydrocarbons.
800 The best correlations to be used for hydrogen content calcula-
ft3std/bbl

tions were the following:

600

400 For HDS of naphtha: JenkinsWalsh

For HDS light and heavy gasoils: Dhulesia
200
For HDT of AR and VR: Goosens
0
0 10 20 30 40 50 60 70
All of them presented deviation from experimental hydrogen
Feedstock API gravity
consumption in the range of 915%. This behavior corresponds
Fig. 2. Hydrogen consumption by global hydrogen balance with experimental data. more or less to the range of application reported by the authors.
3600 L.C. Castaeda et al. / Fuel 90 (2011) 35933601

4.3. Hydrogen balance in gas streams 800

Hydrogen consumption, ft3std/bbl

Experimental Lee Stratiev-Tzingov
700
The hydrogen balance in gas streams was performed with
the amount of hydrogen entering and leaving the reactor as well 600

as the amounts of hydrogen dissolved in the liquid, hydrogen 500

contained in H2S, and hydrogen contained in C1C6 hydrocar-
400
bons determined experimentally by GC and molar equivalents
calculations. 300
The amount of dissolved hydrogen for all fractions was rela- 200
tively low because the conditions at storage container of HDT li-
quid product are close to ambient and the solubility of hydrogen 100
is strongly dependent of pressure and temperature. The value of 0
hydrogen dissolved in the hydrotreated liquid stream was not ob- HDSN HDSD HDSG
tained experimentally, but only by using two different correlations,
Fig. 5. Hydrogen consumption by chemical reactions.
the detailed calculation was not considered appropriate to be in-
cluded in this manuscript.
Fig. 4 shows for all the hydrotreated fractions the hydrogen con-
1400
sumption obtained from hydrogen balance in gas streams, the dis-

Hydrogen consumption,
1200 Experimental Edgar-Speight
solved hydrogen from correlations and calculations using Hysys
simulator. 1000

ft3 std/bbl
The dissolved hydrogen from KorstenHoffman and Mapiour 800
Sundaramurthy correlations and that determined by Hysys led to 600
similar results. Hydrogen consumption determined from Eq. (5) 400
showed deviations lower than 0.23% respect to the global hydrogen
200
balance on the HDT of light and heavy gasoils, while the observed
0
error in the HDT of heavy fractions was between 1.14% and 2.73%. HDSN HDSD HDSG HDAR HDVR
In general, hydrogen consumption calculated from the hydrogen
balance in gas streams is close to that obtained by the global Fig. 6. Hydrogen consumption by reactions average contribution.
hydrogen balance.
The dissolved hydrogen accounts for 0.16% of total hydrogen
consumption from hydrogen balance in gas streams as expressed underpredicted the hydrogen consumption and they have the low-
by Eq. (2). This certainly not a high contribution, is the most likely est error for HDS of light gasoil, which is in agreement with their
reason why reners use the difference between the amount of range of application.
hydrogen entering and leaving the reactor in the gas streams,
DHgas, to report the hydrogen consumption. 4.5. Hydrogen consumption by reaction average contributions

EdgarSpeight approach was developed to calculate the hydro-

4.4. Class of hydrogen-consuming chemical reactions
gen consumption in HDT as function of feedstock and product
properties.
Correlations of Lee and StratievTzingov were used to estimate
Fig. 6 presents the hydrogen consumption estimated by using
the hydrogen consumption from the properties of liquid streams
EdgarSpeight method and its comparison with the experimental
entering and leaving the reactor. These correlations, which are sim-
value from the global hydrogen balance. The predictions are clearly
ilar and dependent on feedstock and product properties, were
better for HDT of heavy feed. The error for HDS of light petroleum
developed for HDT of light gasoils.
fractions is higher than 50%.
Hydrogen consumption calculated from these correlations was
compared with that obtained from the experimental global hydro-
gen balance. The results are shown in Fig. 5. Hydrogen consump- 5. Conclusions
tion for HDS of AR and VR is not presented because these
correlations do not include contributions of the HDM and hydro- The accurate hydrogen consumption cannot be directly mea-
cracking reactions. In general, it is observed that the correlations sured 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 under-
estimate it in about 6%. Hydrogen balance, which includes ow
Hydrogen consumption, ft3 std/bbl

Experimental Korsten-Hoffman
rate data, GC analysis, liquid analysis and dissolved hydrogen cal-
Mapiour-Sundaramurty Hysys
culations is required to determine the real H2 consumption.
The best correlations to be used for hydrogen content calcula-
tions in liquid streams were the following: JenkinsWalsh correla-
tion 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
HDSN HDSD HDSG HDAR HDVR
chemical reactions contributions for HDT middle fractions, while
Fig. 4. Hydrogen consumption by hydrogen balance in gas stream with correlations the approach developed by Edgar and Speight is better for heavy
for dissolved hydrogen. fractions.
 L.C. Castaeda et al. / Fuel 90 (2011) 35933601 3601

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