China Petroleum Processing and Petrochemical Technology

Process Research 2012,Vol. 14, No. 1, pp 1-7 March 30, 2012

Medium-Pressure Hydro-upgrading (MHUG) Technology

for Producing Clean Diesel Fuel
Jiang Donghong; Zhang Yuying; Hu Zhihai; Nie Hong
(Research Institute of Petroleum Processing, Beijing 100083)

Abstract: This article introduces the development and application of the medium-pressure hydro-upgrading (MHUG) tech-
nology developed by the Research Institute of Petroleum Processing (RIPP). The MHUG technology based on the chemistry
of diesel hydro-upgrading reactions has the advantages of flexible product slate and excellent product quality that can in-
crease the cetane rating of diesel fuel up to more than 15 units. The hydrotreating and hydro-upgrading catalysts associated
with the MHUG technology have outstanding performance to meet the demand of MHUG technology for hydro-saturation
and selective ring-opening of aromatic rings. New MHUG process flow scheme can further increase the yield and selectivity
of target products. Commercial application of multiple MHUG units has revealed that the MHUG technology designated for
clean diesel production features good feedstock adaptability and operating stability.
Key words: medium-pressure hydroupgrading; MHUG technology; catalyst; cetane number; clean diesel fuel

1　Introduction drocarbon emissions in exhaust gas; and (3) limiting aro-

With the fast development of China’s national economy
the vehicle emission regulations and relevant automotive
gasoline and diesel quality standards are being continu-
ously upgraded. Starting July 1st, 2011 China enforced
nationwide the diesel quality standard GB 19147—2009
which is equivalent to the Euro III diesel quality standard.
However, beginning from January 1st, 2008 the Beijing
Municipal Government has been first of all enforcing
the diesel quality standard DB 11/239—2007 which is
equivalent to the Euro IV quality standard, and plans to
pursue more stringent automotive diesel standard that will
consistent with the Euro V diesel quality standard, attest-
ing to demand for an accelerated process to manufacture
clean diesel fuel.
The tasks for manufacture of clean diesel fuel mainly
cover the following aspects, i. e.: (1) reduction of sulfur
content in diesel fuel, because sulfur compounds con-
tained in diesel could greatly increase the emission of
particulate matter in vehicle exhaust gas and deactivate
the three-way catalytic converter; (2) increase of cetane
rating of diesel, because the cetane rating of diesel fuel
not only can affect the noise level and fuel consumption
of diesel vehicle, but also can influence the NOx and hy-
matics especially polynuclear aromatics in diesel, because
polynuclear aromatics in diesel can apparently increase
the emission of particulate matter in vehicle exhaust gas
to aggravate exhaust pollution.
In order to meet the demand for production of clean die-
sel fuel, RIPP had developed in the early 1990s the first-
generation medium-pressure hydro-upgrading (MHUG)
technology[1]. The MHUG technology adopts a single-
stage process using hydrofining/hydro-upgrading cata-
lysts that differ in catalytic functions for processing FCC
gas oil (LCO), straight-run gas oil (SRGO), coker gas
oil (LGCO), and vacuum light distillate (LVGO) or their
mixture to manufacture low-sulfur, low aromatic content
and high cetane rating diesel, jet fuel and naphtha with
high potential aromatic content through selective ring-
opening and cracking of aromatics[2].
The technical performance of MHUG technology has
been improving with an ever deepening development of
this technology. The uninterruptedly progressing MHUG
technology can under appropriate process conditions pro-
duce clean automotive diesel fuel with a sulfur content
Corrresponding Author: Mr. Jiang Donghong, E-mail: jiangdh.
ripp@sinopec.com.

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China Petroleum Processing and Petrochemical Technology
less than 10 μg/g and a cetane rating higher than 51 and
naphtha with high potential aromatic content from inferior
gas oil with low cetane number, and the increase in cetane
rating of gas oil can reach as high as more than 15 units.
2　
Reaction Chemistry Involved in the
Medium-Pressure Hydro-upgrading
Process
One of the main purposes of MHUG process is to signifi-
cantly increase the cetane number of gas oil feedstock.
The cetane rating of diesel fuel depends upon its chemical
composition and distillation range. Figure 1 presents the
influence of different hydrocarbon group compositions
and carbon numbers on cetane number of distillates [3].
The approximate relationship between different hydrocar-
bons and their cetane rating is as follows. Among differ-
ent hydrocarbons with the same carbon number alkanes
have the highest cetane number, and olefins, iso-paraffins
and cycloalkanes occupy the middle place, whereas aro-
matics, in particular polynuclear aromatics and polycyclic
naphthenes, have the lowest cetane number. The higher
the degree of isomerization of hydrocarbons and the more
their number of rings, the lower their cetane rating would
be. The cetane number of naphthenic and aromatic hydro-
carbons increases with an increasing length of their side
chains, and decreases with an increasing degree of their
branched side chains.
FCC gas oil is rich in aromatics that account for 50%-
90% of its hydrocarbon composition, and the aromatics
are mostly composed of bicyclic and polycyclic aromatics
accounting for over 60% of total aromatic hydrocarbons.
Furthermore, since bicyclic and polycyclic aromatics have
very low cetane number, the study on technology for in-
creasing cetane rating of diesel fuel should be emphasized
to enhance the cetane rating of polynuclear aromatics.
In general, the hydrodesulfurization, hydrodenitrogena-
tion and aromatics saturation reactions take place in the
course of hydrotreating reactions. Study has revealed
that the bicyclic and higher aromatic hydrocarbons con-
tained in gas oil obtained during RFCC process can be
converted at a high rate during hydrotreating reaction,
but hydrosaturation reaction of monocyclic aromatics is
readily controlled by thermodynamic equilibrium and the
reaction rate is quite small, leading to a insignificant total
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2012,14(1):1-7
Figure 1　Cetane number of different hydrocarbons
■—n-Alkane; ●—Olefin; — —i-Alkane; — —Aromatics;
— —Monocyclic naphthene; — —Dekalin;
— —Tetralin; — —Naphthalene
aromatics saturation rate under conventional hydrotreating
conditions[4]. The main products obtained after aromat-
ics saturation reactions include such low cetane-number
components as dekalins, tetralins or indenes, and the
magnitude of cetane rating increase is not remarkable.
In contrast to boosting cetane number by means of simple
hydrosaturation of aromatics, the selective ring-opening
reaction taking place during partial hydrosaturation of
aromatics, in particular polynuclear aromatic hydrocar-
bons, can result in a more remarkable increase in cetane
number of the product as evidenced by an increasing
number of research reports [5]. Therefore, the MHUG
technology draws up a reaction pathway encompassing
saturation of polynuclear aromatic hydrocarbons followed
by ring-opening through hydrocracking of these relevant
hydrocarbons. Figure 2 presents the reaction pathway for
hydrogenation of bicyclic aromatics that are dominant in
FCC gas oil. The steps (1)→(2) denote the hydrotreating
reaction pathway, while the steps (1)→(3)→(4) denote
the reaction pathway involved in the hydroupgrading
(MHUG) process. Under the hydrofining reaction condi-
tions, the relative reaction rate constant for the step (2) is
very low and is easily affected by thermodynamic equi-
librium, which can constrain the total aromatics conver-
sion. Nevertheless, the MHUG technology has designed a
step (3) to ensure a relatively fast reaction rate occurring
on acidic hydroupgrading catalyst that is not constrained
by thermodynamic equilibrium to break the limitation
imposed by thermodynamic equilibrium on hydrosatu-
ration of whole bicyclic aromatic hydrocarbons, which
can ensure successful proceeding of reactions along the
 Jiang Donghong, et al. Medium-Pressure Hydro-upgrading (MHUG) Technology for Producing Clean Diesel Fuel

steps (1)→(3)→(4) to effectively modify the hydrocarbon 3　

Catalysts and Process Flow Diagram
group composition of gas oil and increase the ideal hydro- of MHUG Technology
carbon constituents in diesel fraction.
3.1　Catalysts for MHUG technology
In order to achieve the goal for medium-pressure hydro-
upgrading of gas oil the high-performance hydrogenation
catalysts are urgently required. The key for success of the
MHUG technology is the catalysts. The MHUG technol-
Figure 2　Reaction pathway for hydrogenation of bicyclic
ogy employs two kinds of main catalysts, among which
aromatics
one is a hydrotreating catalyst with good hydro-denitroge-
Table 1 presents the change in hydrocarbon group com- nation and aromatics saturation activity and the other one
position after hydroupgrading of low cetane-number gas is a hydrocracking catalyst with high ring-opening and
oil feed by means of MHUG technology. It can be seen cracking selectivity. The hydrotreating catalyst is used to
from Table 1 that the density of diesel fraction obtained take part in the HDS, HDN and HDA reactions, while the
after processing the feedstock by MHUG technology hydrocracking catalyst is employed for taking part in the
has been significantly reduced coupled with a staggering ring-opening and cracking reactions in order to reduce the
increase in its cetane rating. The content of alkanes in cyclic hydrocarbons content in the hydrogenate.
diesel fraction had increased by 13% as compared to that The catalyst used in the hydrotreating section can promote
in the feedstock, and the total aromatics removal rate had the HDS, HDN and HDA reactions in the course of hy-
reached 81.27%, while the removal of polynuclear aro- droupgrading to provide the hydrocracking catalyst with
matics had reached as high as 98.96%. The data listed in necessary preparations for performing ring-opening and
Table 1 have been in good agreement with those referred cracking reactions. Table 2 lists the comparison of HDS,
to by the hydroupgrading reaction pathway realized by HDN and aromatics hydrogenation performance between
the MHUG process. the hydrotreating catalyst RN-32V for the MHUG tech-
nology developed by RIPP and a reference catalyst under
Table 1　Change in cetane number and hydrocarbon
the same reaction conditions for treating the same feed
group composition between gas oil feed and
hydro-upgraded diesel product
oil. It can be seen from the data listed in Table 2 that the
Gas oil Diesel
hydrotreating catalyst RN-32V had a better hydrotreating
Property
feed product performance as compared to the reference catalyst, with
Density (at 20 ℃), g/cm3 0.8876 0.8286 its relative HDS activity and relative HDN activity equat-
Cetane number 31.2 46.5 ing to 236% and 138% of that achieved by the reference
Hydrocarbon group composition, % catalyst, respectively.
Alkanes 20.3 33.3 Table 2　Performance of catalyst RN-32V used in the
Total naphthenes 35.1 58.8 hydrotreating section of MHUG process
Total monocyclic aromatics 23.0 7.7 Reference
Catalyst RN-32V
catalyst
Total bicyclic aromatics 16.7 0.2
S content in product, μg/g 57 12
Total tricyclic aromatics 2.5 0.0
N content in product, μg/g 8 1
Resins 2.4 0.0
Total aromatic content of product，% 22.0 20.9
Total aromatics removal rate, % 81.27
Relative desulfurization activity 100 236
Rate for removal of bicyclic and higher
98.96
aromatics, % Relative denitrogenation activity 100 138
Note: Hydrogen partial pressure during reaction was 9.8 MPa, volumet- Note: Sulfur content in feed oil was 1.8%, and nitrogen content in feed
ric space velocity (on main catalyst) was equal to 0.8 h-1, and the reac- oil was 1 200 μg/g, with the total aromatics content equating to 42.0%
tion temperature was the base value. in the feed oil.

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China Petroleum Processing and Petrochemical Technology
The selective ring-opening and cracking catalyst applied
in the MHUG technology must have good aromatics satu-
ration activity that can convert aromatics into cyclanes
along with good selective ring-opening activity, so that
the catalyst apart from changing the composition of die-
sel fraction and significantly boosting the cetane number
of diesel can reduce the ratio of secondary cracked by-
products to ensure high diesel yield. The performance of
the MHUG series hydro-upgrading catalysts developed
by RIPP is presented in Figure 3 and Figure 4. To meet
the demand of different users it is proposed to select in-
dividual hydro-upgrading process schemes with associ-
ated catalysts to maximize the diesel yield along with co-
production of the reformer feedstock.
Figure 3　Cetane rating boosting performance of the MHUG
series hydroupgrading catalysts
—RHC-5 catalyst; ■—RT-5 catalyst;
▲—RIC-2 catalyst; ●—RIC-1 catalyst
Figure 4　Reaction activity of the MHUG series
hydroupgrading catalysts
—RHC-5 catalyst; ■—RT-5 catalyst;
▲—RIC-2 catalyst; ●—RIC-1 catalyst
It can be seen from Figure 3 that among the MHUG se-
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2012,14(1):1-7
ries hydroupgrading catalysts the RIC-2 catalyst has the
highest reaction temperature-cetane number boosting
performance, albeit with lower hydrocracking activity as
compared to that of the RHC-5 catalyst, and this catalyst
is suitable for the hydro-upgrading case for maximizing
the diesel yield. On the other hand, the RHC-5 catalyst
having a higher hydrocracking conversion capability is
suitable for the hydro-upgrading case aimed at manufac-
ture of diesel with coproduction of the reformer feed.
3.2　Process flow diagram of MHUG technology
Depending upon the production targets, the MHUG
technology can adopt a variety of flexible process flow
diagrams. The traditional process flow diagram of MHUG
technology is shown in Figure 5. It can be seen from Fig-
ure 5 that this process flow scheme is similar to that of the
single-step hydrocracking unit provided with two cata-
lysts connected in series, with the major equipment com-
posed of the reaction system, the fresh hydrogen system,
the recycle hydrogen system and the fractionation sys-
tem. The hydrotreating catalyst and the hydroupgrading
catalyst can be either loaded in the same reactor or can
be loaded separately in two different reactors, with each
catalyst being distributed in two or more catalyst beds.
In order to increase the selectivity of hydroupgrading pro-
cess for maximization of product yield, RIPP has devel-
oped a series of new MHUG process flow diagrams. One
new MHUG process flow diagram presented in Figure
6 intends to recycle a part of the kerosene fraction boil-
ing between 175 ℃ and 250 ℃ to increase the yield and
selectivity of naphtha to be used as the reformer feed and
concurrently to remarkably boost the cetane number of
the diesel fraction. Table 3 depicts the reaction outcome
of MHUG technology realized according to the traditional
process flow scheme in comparison with the new process
flow scheme aimed at increased production of the reform-
er feed.
It can be seen from the data listed in Table 3 that applica-
tion of the improved MHUG process flow diagram for in-
creasing the reformer feed yield can significantly increase
the yield of heavy naphtha to be used as high-quality
reformer feed while harvesting a higher cetane rating of
diesel product.
Jiang Donghong, et al. Medium-Pressure Hydro-upgrading (MHUG) Technology for Producing Clean Diesel Fuel

Figure 5　Principle process flow diagram of traditional MHUG technology

Figure 6　Improved MHUG process flow diagram for increasing naphtha yield and selectivity

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China Petroleum Processing and Petrochemical Technology 2012,14(1):1-7

Table 3　Reaction outcome of improved NHUG process 4　Commercial Application

flow diagram for increasing catalytic reformer feed
Conventional Improved The MHUG technology has been applied at over 15
Item process flow process flow commercial units since its successful development. The
scheme scheme
commercial application status of the MHUG technology
Is the specified kerosene fraction recycled? No Yes
is presented in Table 4. The outcome of commercial ap-
Heavy naphtha (reformer feed) yield, % 22.85 28.64 plication of the MHUG technology has revealed that this
Diesel fraction yield, % 74.50 64.20 technology can manufacture low-sulfur and high-cetane-
Property of heavy naphtha number clean diesel from various inferior gas oil feed-
S content, μg/g <0.5 <0.5 stocks coupled with excellent feedstock adaptability and
operating stability.
N content, μg/g <0.5 <0.5
In April 2009 a 3.6-Mt/a hydro-upgrading unit de-
Br number, gBr/100g <0.5 <0.5
signed and constructed using the MHUG technology at
Potential aromatic content, % 65.3 63.2
CNOOC’s Huizhou refinery, as the largest in the world
Property of diesel product single hydro-upgrading unit, was successfully put on
S content, μg/g <10 <10 stream while cranking out qualified petroleum products.
Cetane number 51.9 56.5 It can be seen from Table 5 that after adoption of the
Polynuclear aromatics content, % 0.3 0.5
MHUG technology the 3.6 Mt/a hydro-upgrading unit at
CNOOC’s Huizhou refinery can be able to directly de-
Note: Hydrogen partial pressure during reaction was 8.0 MPa, volumet-
ric space velocity based on fresh feed (on main catalyst) was 0.8 h-1, and liver diesel fuel meeting the Euro V emission standard,
reaction temperature was the base value. with the sulfur content in diesel product equating to less

Table 4　Achievements of RIPP in commercial application of hydroupgrading technology

Sequential No. Refineries applying this technology Pressure rating, MPa Production scale, kt/a Feedstock

1 PetroChina Daqing Petrochemical Company 8.0 120 LCO+LVGO

2 PetroChina Jinzhou Petrochemical Company 8.0 800 LCO+SRGO

3 SINOPEC Wuhan Branch Co. 8.0 400 LCO

4 SINOPEC Yanshan Branch Co. 10.0 1 300 LCO+VGO

5 PetroChina Jinzhou Petrochemical Company 8.0 1 100 LCO+SRGO

6 SINOPEC Luoyang Branch Co. 8.0 800 LCO

7 PetroChina Jinzhou Petrochemical Company 8.0 1 100 LCO+SRGO

8 SINOPEC Yanshan Branch Co. 8.0 1 000 LCO+SRGO

9 SINOPEC Luoyang Branch Co. 8.0 800 LCO+LCGO

10 Coal liquefaction project of the Shenhua Group 13.0 1 000 Coal Liquefied Oil

11 CNOOC’s Huizhou Refinery project 12.0 3 600 SRGO+LCO

12 SINOPEC Zhanjiang Dongxing Co. 10.0 1 500 SRGO+LCO

13 North Petrochemical Co., Ltd. 8.0 600 LCGO

14 SINOPEC Jinan Branch Co. 8.0 800 LCO+LCGO

15 SINOPEC Tahe Branch Co. 8.0 1 000 LCGO+SRGO

16 CNOOC Asphalt Co., Ltd. 10.0 800 LCGO+SRGO

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 Jiang Donghong, et al. Medium-Pressure Hydro-upgrading (MHUG) Technology for Producing Clean Diesel Fuel

Table 5　Calibration of operating status of 3.6 Mt/a MHUG unit at CNOOC’s Huizhou refinery

Property item Feedstock Light naphtha Heavy naphtha Kerosene Diesel

Mass yield，% - 6.53 21.75 28.49 41.75

Density (at 20 ℃), g/cm3 0.8637 0.6517 0.7629 0.8077 0.8248

S content, μg/g 1721 - <0.2 <0.5 <10.0

N content, μg/g 187.2 <0.2 <0.2 <0.5 <0.5

Boiling range, ℃ 179—356 26—86 88—168 152—218 207—343

Smoke point, mm - - - 25.8 -

Freezing point, ℃ - - - <-60 -

Potential aromatic content, % - - 61.0 - -

Cetane number 36.8 - - - 53.9

Increase in cetane number - - - - 17.1

Polynuclear aromatics content, % 16.7 - - - 0

Note: Hydrogen partial pressure during reaction=10.8 MPa, volumetric space velocity (on main catalyst)=1.29 h-1, and temperature in hydrofining re-
actor/hydroupgrading reactor= 356 ℃/353 ℃.

than 10 μg/g and its cetane number reaching 53.9 without
any polynuclear aromatics content. The smoke point of
kerosene product is higher than 25 mm which can be used
as a qualified jet fuel. The heavy naphtha, the yield of
which reaches 21.75%, has low nitrogen content and high
potential aromatics content, and can be directly used as an
excellent reformer feed.
5　Conclusions
from inferior gas oil feedstocks at the refinery.
References
[1]　Shi Jianwen, Shi Yulin, Nie Hong, et al. Study and applica-
tion of medium-pressure hydroupgrading catalysts and pro-
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[2]　Shi Yulin, Shi Jianwen, Zhang Xinwei, et al. MHUG pro-
cess for production of low sulfur and low aromatic diesel

In the early 1990s RIPP after having on the basis of hy- fuel[C/CD]. NPRA Annual Meeting, AM-93-56. San Anto-

droupgrading reaction chemistry developed the medium- nio, TX. 1993

pressure hydroupgrading (MHUG) technology has been [3] Odette T. Eng, James E. Kennedy. FCC light cycle oil: li-
　

uninterrupted working on the improvement of catalysts
and process technology to make the MHUG technology
flexible in product slate coupled with delivery of qualified
products.
Ample results of application of MHUG technology have
revealed that the MHUG technology features good feed-
stock adaptability and high operating stability along with
delivery of qualified products, and is an ideal technique
for manufacturing either clean diesel or clean diesel with
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[5]　Brian Watkins, David Krenzke, et al. Distillate Pool
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CD]. NPRA Annual Meeting, AM-10-166. Phoenix, AZ.
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