China Petroleum Processing and Petrochemical Technology

Simulation and Optimization 2013, Vol. 15, No. 2, pp 67-73 June 30, 2013

Application of Discrete Lumped Kinetic Modeling on

Vacuum Gas Oil Hydrocracking
Han Longnian1; Fang Xiangchen2; Peng Chong2; Zhao Tao1
(1. Liaoning Shihua University, Fushun, Liaoning 113001;
2. SINOPEC Fushun Research Institute of Petroleum and Petrochemicals)

Abstract: The kinetic model of vacuum gas oil (VGO) hydrocracking based on discrete lumped approach was investigated,
and some improvement was put forward at the same time in this article. A parallel reaction scheme to describe the conver-
sion of VGO into products (gases, gasoline, and diesel) proposed by Orochko was used. The different experimental data
were analyzed statistically and then the product distribution and kinetic parameters were simulated by available data. Fur-
thermore, the kinetic parameters were correlated based on the feed property, reaction temperature, and catalyst activity. An
optimization code in Matlab 2011b was written to fine-tune these parameters. The model had a favorable ability to predict
the product distribution and there was a good agreement between the model predictions and experiment data. Hence, the ki-
netic parameters indeed had something to do with feed properties, reaction temperature and catalyst activity.
Key words: hydrocracking; kinetic modeling; vacuum gas oil (VGO); optimization code; parallel reaction scheme

1　Introduction incorporate the fixed lumped models, discrete lumped

Faced with a growing demand for middle distillate and
an increasing production of heavy crude oils, the hydro-
cracking process has become one of the most important
secondary petroleum refining processes. This process is
versatile, flexible and can be strongly adapted to inferior
feed oil with a strong capability to convert the heavy,
high-boiling, and high EBP (end boiling point) feedstock
to smaller, lower-boiling ones like qualified jet fuel, die-
sel, lubrication base oil, and naphtha for chemical use[1].
Hydrocracking takes place over a dual-functional catalyst
in a hydrogen-rich, high temperature atmosphere, with
other reactions, including hydrodesulfurization, hydrode-
nitrogenation and other hydrotreating reactions, occur-
ring simultaneously[2]. Despite the successful application
of hydrocracking technology in commercial scale, the
research on its reaction mechanism and reaction kinetics
still lags behind the customer needs.
There are various kinetic models for the VGO hydro-
cracking reported in the literature, and the lumped model
and detailed molecular model[3] are regarded as two main
approaches being studied for a long time. Moreover, all
of the hydrocracking kinetic models could be included
in the two approaches. Among them, the lumped models
models [4-7] and continuous mixtures involved lumped
models[8-10]. For the hydrocracking models based on the
lumping technique, these physical properties such as true
boiling point (TBP), carbon number (CN), and molecular
weight[11] are usually adopted to divide discrete pseudo-
components (lumps). For the fixed lumped model and
discrete lumped model, the major disadvantage is that a
change in the cutting scheme of the hydrocracker prod-
ucts or in the number of products requires reformulating
the model parameters to refit the data. The so-called con-
tinuous lumped model is a general case developed from
the discrete lumped model, which allows for prediction of
the entire distillation curve, but the dependency of model
parameters on feed properties still exists. Furthermore,
the distillation curves of heavy oils are not accurate when
the feedstock is a mixed oil consisting of VGO, CGO,
DAO and other fractions. Detailed approaches include the
structure oriented lumped models[12] and the single event
models[13-14], which express the chemical transformations
in terms of typical molecular structures and elementary
Recieved date: 2012-12-27; Accepted date: 2013-02-05.
Corresponding Author: Professor Fang Xiangchen, E-mail:
fangxiangchen.fshy@sinopec.com.

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China Petroleum Processing and Petrochemical Technology 2013,15(2):67-73

steps of cation chemistry, respectively. For a relatively
large number of pseudo-components the analytical infor-
mation and experimental data are required, which impose
restrictions on their applications to hydrocracking of real
feedstocks.
The complexity of real feedstocks suggests that lumped
model will continue to be used for the research on VGO
hydrocracking kinetics. However, detailed approaches
need to be studied more precisely in order to obtain a bet-
ter understanding of hydrocracking kinetics and provide
an idea to optimize lumped model for prediction of hy-
drocracking product properties. A good kinetic model is
a useful tool for reactor design, simulation, and optimiza-
tion of oil refining processes.
To have a better understanding of the VGO hydrocrack-
ing, in this work we conducted some experiments in a pi-
lot plant equipped with two downflow fixed-bed reactors
and developed a discrete lumped kinetic model, which
will be presented in further papers.
2　Experimental Data and Kinetic Model
2.1　Experimental setup and feedstock
The experiments were conducted in a single-stage series
fixed-bed high-pressure pilot plant, which is shown sche-
matically in Figure 1. Hydrocracking was conducted in a

Figure 1　Experimental setup for high-pressure hydrocracking experiment

1—Feedstock tank; 2—Oil pump; 3—Hydrotreating reactor; 4—Hydrocracking reactor; 5—Gas-liquid separator; 6—Make-up hydrogen;
7—Recycle hydrogen; 8—Recycle hydrogen compressor; 9—Washing tower

downflow mode of operation. The hydrotreating catalyst
was loaded in a hydrotreating reactor and the hydrocrack-
ing catalyst (A) was loaded in a hydrocracking reactor.
The reactor temperature was controlled at the desired
level by using a three-zone electric furnace providing an
isothermal temperature condition along the reaction sec-
tion. The temperature inside the reactor was measured by
a movable axial thermocouple located inside the reactor.
Three typical heavy VGO samples, including Iranian
VGO, Saudi VGO and mixed oil (Iranian VGO: CGO=8:2
sampled from Zhenhai refinery), were chosen as the feed.
Main properties of these feedstocks are listed in Table 1.
These feedstocks had high density, EBP, BMCI and sulfur
content so that severe hydrogenation operating conditions
were needed in order to achieve the expected conversion
degree and index requirements of product properties. Hy-
drogen gas was provided from an electrolysis hydrogen
source, with the hydrogen purity exceeding 99.9%.

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 Han Longnian, et al. Application of Discrete Lumped Kinetic Modeling on Vacuum Gas Oil Hydrocracking

Table 1　Main properties of feedstock late yield increased when the hydrocracking temperature
Items Iranian VGO Saudi VGO Mixed oil increased from 381 ℃ to 390 ℃ and these results were
Density (20 ℃), g/cm3 0.9130 0.9208 0.9163 consistent with the catalytic activity of the hydrocracking
Distillation, ℃ catalyst A.

IBP/10% 336/379 325/382 327/389 Table 2　Product yield distribution of Iran VGO hydrocracking
30%/50% 409/433 411/435 414/434 Reaction temperature, ℃ 381 385 390

70%/90% 463/506 462/505 462/513 Conversion (>370 ℃), % 65.30 75.80 83.52

95%/EBP 525/542 526/536 536/554 Gases yield, % 1.81 2.12 3.58

3
Density (15.6 ℃), g/cm 0.9169 0.9246 0.9201 Light naphtha (<82 ℃) yield, % 3.53 5.01 6.72
Volume-mean boiling point TV, ℃ 438 439 442.4
Heavy naphtha (82—132 ℃) yield, % 7.51 11.45 14.11
Tm, ℃ 430.84 432.22 435.54
Kerosene (132—282 ℃) yield, % 31.90 38.44 42.87
Kf 11.80 11.71 11.78
Diesel (282—370 ℃) yield, % 20.55 18.78 16.24

2.2　Some properties of hydrocracking catalyst Gasoline yield, % 11.04 16.46 20.83

Middle distillates yield, % 52.45 57.22 59.11

There were several advanced hydrocracking catalysts
with high middle distillate yield, and the hydrocracking
catalyst A was a new generation catalyst developed on 2.4　Kinetic model of VGO hydrocracking
the base of reference catalyst by modifying the support In this study, the kinetic model developed by Orochko[15]
(Si/Al) and Y zeolite, which was a W/Ni commercial was used to simulate the product distribution in hydro-
catalyst employed in the experiments (with a specific sur- cracking process. The hydrocracking kinetics of vacuum
face area of 200 m2/g, a pore volume of 0.28 cm3/g, and gas oil from Iranian crude oils was studied in a fixed-bed
a mean pore diameter of 1.5—1.7 mm). The catalyst A reactor over the hydrocracking catalyst A using a first-
was loaded into the hydrocracker and activated in situ by order kinetic scheme involving four lumps. The reaction
sulfiding with kerosene containing CS2. This catalyst had scheme is shown in Figure 2. Theoretically speaking,
high hydrogenation performance, high middle distillate the four lumped kinetic model schemes should include a
yield, and suitable activity and stability, and demonstrated series of reactions and parallel reactions. But the hydro-
strong adaptability to inferior feedstock. It had been used cracking catalyst A has low cracking activity and rarely
in many hydrocrackers to deliver qualified middle distil- takes part in secondary cracking reaction. So only the par-
lates and hydrocracked residue with low BMCI value. allel reaction of heavy oil cracking was considered in the
model scheme, while ignoring the secondary reactions,
2.3　Experimental data of hydrocracking
namely the formation of diesel lump to gasoline, the gas
Experiments on hydrocracking of Iranian VGO at differ- lump, and gasoline lump to gas lump.
ent conversion rates were carried out under the operating
condition specifying a partial hydrogen pressure of 15.7
MPa, a total LHSV of 1.5 h-1 and a total H2/oil ratio of
1 500:1. Moreover, the nitrogen content of hydrotreated
oil was controlled at around 10 mg/g. The products were
analyzed by true boiling point distillation, with the prod-
uct distribution presented in Table 2. It can be seen from
Table 2 that the VGO conversion increased following the
Figure 2　Reaction scheme for hydrocracking lump-kinetic
increase of reaction temperature, which was accompanied
model
by an increase of kerosene yield but a decrease of diesel
yield. Meanwhile, it is obvious that the middle distil- In this study, gases lump (include LPG and off-test),

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China Petroleum Processing and Petrochemical Technology 2013,15(2):67-73

gasoline lump (light and heavy naphtha), and diesel lump yexp -ymod
ARD = ×100% (5)
(kerosene and diesel) were considered as three of four yexp
lumps. Moreover, the hydrocracker products and yield are 3

shown in Table 2. The experimental data of hydrocrack- OBJ = ∑ ( yexp -ymod ) 2 ×100% (6)
i =1
ing process were used to model the kinetic parameters of in which yexp and ymod are experimental and model yield
hydrocracking reactions. of product, respectively. The ARD and OBJ of model pre-
The hydrocracking process took place according to a dictions are shown in Table 3. It can be seen from Table
retarded first-order reaction, which was the equation de- 3 that the calculation error was small enough to meet the
veloped by Orochko[1]. Based on this method, the yields requirements of the model.
of diesel lump and gasoline lump can be expressed by the
Table 3　Model macrokinetic parameters and standard
total conversion y and macro-kinetic parameters.
'
deviation
(1 − y ) k -(1-y )
Diesel lump yield: Z = (1) Reaction temperature, ℃ 381 385 390
1-k '
Conversion, % 65.30 75.80 83.52
Gasoline lump yield:
'' ' '' Gexp, % 1.81 2.12 3.58
(1 − y ) k -(1-y ) k (1 − y )-(1 − y ) k
X = k' × ' ' ''
+ k' × (2)
(1-k ) × (k -k ) (1-k ' ) × (1-k '' ) Gmod, % 1.809966 2.120228 3.579525
Gases lump yield: G=Y-(Z+X) (3) ARD (G) 1.9029e -5
1.0763e -4
1.3273e-4
in which Z, X, and G are experimental yield of diesel Xexp, % 11.04 16.46 20.83
lump, gasoline lump and gases lump, respectively, and y
Xmod, % 11.03991 16.460169 20.829039
is the conversion rate of VGO. -6 -5
ARD (X) 7.9051e 1.0239e 4.6152e-5
Among them, the macrokinetic parameters (k′ and k″)
Zexp, % 52.45 57.22 59.11
depend on feed properties, process temperature and
Zmod, % 52.450053 57.219603 59.110486
catalyst characteristics. All kinetic model parameters
-6 -6
are determined by experimental data and simulated by ARD (Z) 1.0073e 6.9329e 8.2249e-6

an optimization procedure written in the Matlab 2011b.
Furthermore, the objective function which determines the
optimized model parameters is defined as follows.
OBJ=min[(Zmod-Zexp)2+(Gmod-Gexp)2+(Xmod-Xexp)2] (4)
3　Results and Discussion
3.1　Calculation of kinetic modeling parameters
The operating conditions and experimental data of a pilot-
plant scale hydrocracker were used to calculate and vali-
date the model parameters. The results of fine-tuning are
shown in Table 3. By using these parameters, the product
distribution can be calculated. A comparison between
the model results for predicting the product yields is also
shown in Table 3. It can be seen from Table 3 that there
was an extraordinarily good agreement between model
prediction results and experimental data. The absolute
relative deviation (ARD) and mean square error (OBJ) of
the model for predicting the product yields are defined as
follows:
OBJ 1.1594e-12 2.3784e-11 1.3863e-10
k′ 0.3624 0.3324 0.3081
k″ 0.3969 0.2268 0.2278
Since k′ and k″ are kinetic factors with similar meaning
to the rate constants, the relation between macrokinetic
parameters and reaction temperature based on the Arrhe-
nius equation should be studied. The correlation between
-ln(k′, k″) and 1/T is presented in Figure 3. It can be obvi-
ously seen that the macrokinetic parameter k′ could sat-
isfy the Arrhenius equation along with high related coef-
ficient (R2=0.9905), but there was not a close relationship
between macrokinetic parameter k″ and reaction tempera-
ture because of its relatively low coefficient (R2=0.6899).
It might occur because the model parameter (k″) was
not only a function of reaction temperature, but was also
related with other process conditions. This experiment
studied only the process conditions of different reaction
temperatures so that the complete correlation could not be
fully reflected. Perhaps, a further research work needs to

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 Han Longnian, et al. Application of Discrete Lumped Kinetic Modeling on Vacuum Gas Oil Hydrocracking

be accomplished. Through correlation and selection of various methods, the

Figure 3　Relationship between -ln(k′, k″) and 1/T
two empirical model correlations were chosen, which was
an innovative idea adopted in this paper. The empirical
correlations about k′ and k″ are listed as follows:
 X 
k ' = A1× exp  f  + A2 × TV + A3 × K f (11)
T ×w
 X 
k '' = B1× exp  f  + B 2 × TV + B3 × K f (12)
T ×w
where A1, A2, A3, B1, B2, and B3 are model parameters,
which are calculated from the experimental data; w is the
zeolite content in catalyst.
The hydrocracking experiments were carried out on dif-
ferent feedstocks, with the reaction temperature and
experimental data shown in Table 4. Firstly, the mac-
rokinetic parameters (k′ and k″) were calculated from
experimental data listed in Table 4 and then the model
parameters were correlated by the nonlinear least square
method described in the Matlab 2011b. According to the
calculated value listed in Table 4, the macrokinetic pa-
rameters (k′ and k″) optimized from experimental data of
three typical feedstocks were suited quite well to imple-
menting the model calculation because of its low OBJ.

Table 4　Hydrocracking experiments on different

3.2　Correlation of kinetic modeling parameters feedstocks and kinetic parameters
[7]
It has been referred to in the previous research that the Feedstock Iranian VGO Saudi VGO Mixed VGO
macrokinetic parameters (k′ and k″) depend upon the
Conversion (>370 ℃)，% 75.80 83.33 82.42
feedstock property, the reaction temperature, and the na-
ture of catalyst. Furthermore, k′ and k″ are kinetic factors Reaction temperature, ℃ 385 380 392

with similar meaning to the rate constants. Gas yield, % 2.12 3.26 4.27
So a correlation function was put forward to calculate Gasoline yield, % 16.46 21.47 18.19
the macrokinetic parameters. Among them, the charac-
Middle distillate yield, % 57.22 58.60 59.96
teristic factor (Kf) and the volume-mean boiling point
(Tv) functioned as factors which could mainly represent k′ 0.3324 0.3164 0.2956

the feedstock property. The weight percent conversion of k″ 0.2268 0.2035 0.3204
VGO (Xf), reaction temperature (T), and zeolite content of OBJ 2.3784e -11
5.5592e -12
7.3715e-11
catalyst are also included in this empirical correlation. Kf
and TV are calculated by the following formulas and the And then the model parameters describing the relation-
calculated results are listed in Table 1. ship between macrokinetic parameters and feedstock
d15.6=0.99417d20 +0.009181 (7) properties, catalyst activity, and reaction temperature were
Tv=(T10+T30+T50+T70+T90)/5 (8) simulated by an optimization procedure written in the
Tm=TV+5.7715-6.7083×(T90-T10)/80-19.32×100/TV + Matlab 2011b. The objective function which determines
14.913×(T90-T10)/80×100/TV+3.6694×[(T90-T10)/80]× the optimized model parameters is defined as mentioned
(100/TV)2-6.2278×[(T90-T10)/80]2×100/TV (9) previously. Judging from the optimization results listed in
1/3
Kf=1.216×(Tm +273.15 ) /d15.6 (10) Table 5, it has good prediction accuracy which is appro-

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China Petroleum Processing and Petrochemical Technology 2013,15(2):67-73

priate enough for meeting the model not only in terms of

the ARD value but also the OBJ value.

Table 5　Model parameters of macrokinetic

parameters (k′, k″)
Model parameters A1 A2 A3

k′ 2.6367 -0.0083 0.1106

OBJ 5.3897e-14

Model parameters B1 B2 B3

k″ -14.8052 0.0245 0.3763

Figure 5　Model gasoline yield versus experimental gasoline
OBJ 3.0939e-12 yield

But the model estimation relating to the gasoline lump

3.3　Validation of kinetic modeling
and the gas lump was less reliable than the diesel lump
After the kinetic modeling parameters were calculated especially with respect to the gas lump. Furthermore, the
from the above-mentioned experimental data, the kinetic kinetic modeling cannot realize prediction when the prod-
model could be written as follows: ucts cutting scheme was changed.
 X  So far there would not be a model that can realize the pre-
'
k = 2.636 7exp  f  -0.008 3TV + 0.110 6 K f (13)
T ×w diction on different catalysts, feedstocks, and other fac-
 X  tors. Despite the vast commercial application prospects of
k '' = -14.805 2exp  f  + 0.024 5TV + 0.376 3K f (14)
T ×w hydrocracking catalyst A, this model also does not have
'
(1 − y ) k -(1-y ) practicability for industrial hydrocrackers because of con-
Diesel lump yield: Z = (15)
1-k ' straints related with internal diffusion, external diffusion
Gasoline lump yield: and other factors.
'' ' ''
(1 − y ) k -(1-y ) k (1 − y )-(1 − y ) k In general, this model can be only suitable for prediction of
X = k' × ' ' ''
+ k' × (16)
(1-k ) × (k -k ) (1-k ' ) × (1-k '' )
the hydrocracking catalyst at some extent. There is still a long
Gas lump yield: G=Y-(Z+X) (17)
way to establish a perfect kinetic model of hydrocracking.
By using these modeling parameters, the hydrocracking
product distribution can be calculated. The comparison 4　Conclusions
between the calculated results and the experimental data
(1) In this article, a discrete lumped kinetic approach was
are shown in Figures 4—5. It can be seen from the data
depicted in Figures 4—5 that there was a good agreement used to simulate the kinetics of hydrocracking reactions
between model diesel predictions and experimental data. in a pilot-plant hydrocracker. The data sets were statisti-
cally analyzed and then an optimization code was applied
to determine the model parameters. The model prediction
was validated by experimental data and calculated data
based on the model parameters.
(2) Furthermore, the effect of feedstock properties, such
as characteristic factor (K), volume-mean boiling point
(TV), reaction temperature (T) and other parameters were
also correlated in the model. The ARD and OBJ of the
model prediction were calculated and the results verified
the accuracy of the model parameters and model suitabil-
Figure 4　Model diesel yield versus experimental diesel yield ity for predicting the product distribution.

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 Han Longnian, et al. Application of Discrete Lumped Kinetic Modeling on Vacuum Gas Oil Hydrocracking
Acknowledgements: Thanks to the fund of “National ‘Twelfth
Five-Year’ Plan for Science & Technology Support” (No.
2012BAE05B04) and “Research on Hydrocracking Catalysts
Grading Technology” undertaken by Fushun Research Institute
of Petroleum and Petrochemicals (FRIPP) supported by SINO-
PEC (No. 101102).
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