Chemistry and Technology of Fuels and Oils, Vol. 32, No.

6, 1996

PRODUCTION OF DIESEL FUEL WITH IMPROVED

ECOLOGICAL CHARACTERISTICS

K. E. Zeger and V. R. Kotler UDC 665.75:665.658.2

One of the new requirements imposed on diesel fuels is minimal toxicity of the combustion products, as defined by
the contents of sulfur oxides and soot, which must be reduced by respective factors of 3-4 and 2-3. Analysis of the chemical
composition of diesel fuels shows that in order to meet this requirement, it is necessary to lower the content of aromatic
hydrocarbons, particularly polycyclics, by a factor of 2-3, and to lower the sulfur content by a factor of 3-4. This point of view
is reflected in a proposed specification for new diesel fuels produced in a number of countries (Table 1).
Most of the diesel fuel produced in the USA at the start of the 1990s contained up to 0.25% sulfur by weight and up
to 40% aromatic compounds by weight. In the European countries, the diesel fuel that was produced was of a somewhat higher
quality, but it still contained more than 0.2% sulfur and about 30% aromatic hydrocarbons.
Certain developments and concepts in the area of producing diesel fuel with improved ecological characteristics have
been proposed by the firm Topse (Denmark).
As shown by studies performed by this firm, through reduction of the contents of aromatic hydrocarbons and sulfur
compounds in diesel fuel, not only are the amounts of soot and sulfur oxide discharges reduced substantially, but also the cetane
numbers are 5-10 points higher, along with improved distillation characteristics of the fuel.
According to data reported by Texaco, a reduction of the content of aromatic hydrocarbons from 40% to 20% results
in an approximately 15 % reduction of the discharges of nitrogen oxides (Fig. 1). This effect apparently reflects a change in
the conditions of fuel combustion in the engine as a result of increasing its cetane number and reducing the content of difficultly
oxidized high-molecular-weight aromatic compounds.
In line with these concepts, the firm Topse has proposed that in order to improve the ecological characteristics of diesel
fuel, it should be subjected to treatment to remove aromatic and sulfur-containing compounds by means of specially developed
process technologies. In developing these technologies, consideration was given to the availability, in most petroleum refineries,
of process units for catalytic hydrodesulfurization of diesel fuel components; another factor that was considered was the need
for improving the efficiency of these units. To this end, it was recommended that the catalyst volume should be increased (i.e.,
the feedstock space velocity should be lowered) and that the reactor temperature should be increased in order to compensate
for deactivation of the catalyst; it was also recommended that catalysts with higher hydrodesulfurizing activity should be used.
Catalysts for diesel fuel hydrodearomatization have been tested under laboratory and semicommercial conditions. The
tests were performed on a straight-run distillate feed containing 36% sulfur [sic] and 1.7% aromatic hydrocarbons. The types
of aromatic compounds and their contents in the feed were determined by mass spectrometry in combination with high-
performance liquid chromatography (HPLC). These test results are presented in Table 2.
As can be seen from these data, the most suitable catalytic system from the practical point of view is NiW + Pt/A1203.
At a moderate working pressure (4-6 MPa) and a low temperature, this system gives a high degree of dearomatization. The
problem with this system is the very high sensitivity of platinum catalysts to the presence of sulfur in the feed. The feedstock
sulfur content must be no greater than 1-3 ppm. Also, in order to achieve the required conversion of aromatic compounds, the
feedstock space velocity must be less than 0.1 h -1, which is difficult to accomplish in practice.
In the opinion of Topse specialists, a dearomatization catalyst for use in existing hydrotreaters must provide a
satisfactory degree of dearomatization (more than 50%) with a feedstock space velocity greater than 0.5 h-1 and a working
pressure of 6-6.5 MPa, and it must also be sulfur-resistant. Topse's improved sulfur-resistant catalyst (SRC), based on a noble
metal, can operate on feedstocks containing up to 500 ppm of sulfur. This catalyst gives high conversions of aromatic
hydrocarbons at a moderate pressure with a space velocity comparable to that in the single-stage process on NiMo catalyst.

F. t~. Dzerzhinskii All-Russian Heat Engineering Institute (VTI). NOTEKh Joint Stock Company. Translated from
Khimiya i Tekhnologiya Topliv i Masel, No. 6, pp. 15-16, November-December, 1996.

284 0009-3092/96/3206-0284515.00 9 Plenum Publishing Corporation

 TABLE 1

Diesel fuel Maximum i Temperature, ~ Cetane

content T number
production from aromatic
sulfur, hy'hocarbons, IBP EP
wt. % .Ol. %

USA 0,05 35 40
California 0,05 10
EEC 0,05
Sweden
Class 1 0,001 5 180 285 50
Class 2 0,005 20 180 295 47
Class 3 0,05 340--370 43--47
Denmark 0,2 340 50
Japan 0,05

7.12

o
6,58

I
~o 6,04 s g

5,50
10 20 30 40 50
c, vol. %
Fig. 1. Quantity of specific discharges of
nitrogen oxides Q as a function of content
of aromatic compounds in diesel fuel c
(based on test results in a DDAD engine).

Test results on a catalytic system containing the SRC are presented in Table 2. It will be seen that the proposed NiMo
+ SRC system is acceptable in terms of the process conditions and also in terms of achieving the required degree of dearomati-
zation.
Topse's analysis of predicted requirements on diesel fuel quality has demonstrated the future possibility of classifying
diesel fuel on the basis of sulfur content into the following groups: 2-400 ppm, corresponding to a standard limit of 0.05%
sulfur; less than 50 ppm, corresponding to Class 2 fuel in the Swedish classification (see Table 1); and less than 10 ppm.
Starting with the SRC catalyst, two dearomatization catalysts have been developed (TK-907 on an amorphous support,
and TK-908 on a zeolite). The first of these catalysts is recommended for use with feedstock sulfur contents below 10 ppm,
and the second catalyst with sulfur contents of 10-500 ppm. These catalysts were tested in a pilot unit for respective periods
of 1300 and 5500 h. The process was carried out at a moderate temperature and a pressure of about 4.6 MPa on the TK-907
catalyst, and about 5 MPa on the TK-908 catalyst. No deactivation of the catalysts was observed during the test period. The
content of aromatic hydrocarbons in the product was no greater than 5 % for either catalyst, with an aromatics content of 20-
22% in the feed. On the basis of these results, we have been able to recommend the TK-908 catalyst for the production of Class
1 diesel fuel (in the Swedish classification) from low-sulfur feed. Two-year service of this catalyst has confirmed its high
stability. The content of aromatic hydrocarbons in the product was no greater than 5%, with a feedstock content of 17-19%.
Pretreatment of the feed on the high activity NiMo catalyst TK-525 favored the removal of bicyclic and tricyclic compounds.
The TK-907 catalyst has been used in a California refinery for more than 18 months in the production of diesel fuel
from hydrocracker gasoil with a low sulfur content.
On the basis of results obtained in studies by the firm Topse, the following has been proposed for obtaining fuel with
a maximum sulfur content of 0.05 % and an aromatics content of 25-35 % (moderate standards) or below 20 % (rigid standards):
An additional reactor should be installed in parallel with the main reactor (Fig. 2), and an improved catalyst should be used.
Both reactors contain a high-activity NiMo catalyst of the TK-525 type. The total volume of catalyst is increased by
approximately 50%, thus lowering the feedstock space velocity by a factor of approximately 1.5.
The possibilities of implementing this scheme are determined by the capabilities of the existing equipment, in particular
the characteristics of the compressor for the recirculating gas (hydrogen). in order to maximize the consumption of this gas,
the pressure at the inlet to the first reactor should be increased by approximately 1 MPa. When this was done, the consumption

285
 TABLE 2
Hydrodearomatization conditions Degree of
Catalytic system number ~ressure, feedstock dearoma-
of stages dPa temperature SPace tization, -\
velocity, %
h-I
NiMo 1 8--12 Moderate 015-'1,5 30-50
NiMo+NiW 2 8--12 1--2 30--50
NiW+NiW 2 4-6 0,25--0,5 30--50
NiW+ Pt/AI~Oj 2 4-6 Low I 65--80
9 NiMo+SRC 2 4--6 Moderate 0,5-1,5 65-80 .

111

', : ~ 7

II

VII

Fig. 2. Flow plan for obtaining low-sulfur diesel fuel with minimum content of aromatic
compounds: 1) Compressor; 2, 3) added reactor and existing reactor; 4) fired preheater; 5)
cooler; 6) ammonia wash tank; 7) separators; 8) stripping tower; I) hydrogen; II) fuel; Ill) to
treating; IV) hydrogen sulfide; V) off-gas; VI) naphtha; VII) finished product.

,v

v,,I I ~ v,

Fig. 3. Flow plan of two-stage process of catalytic hydrotreating by the Topse method: 1, 9)
Reactors for initial and final hydrotreating, respectively; 2) heat exchanger; 3) reboiler; 4)
cooler; 5) heater; 6) ammonia wash tank; 7) recirculating gas compressor; 8) intermediate
treatment vessel; 10) diesel fuel treatment tower; 11) condenser; I) diesel fuel; II) hydrogen;
III) hydrogen sulfide; IV) steam; V) water; VI) untreated naphtha; VII) finished product; VIII)
heating steam.

of hydrogen increased by approximately one-third (from 20 to 27 m3/m3), the sulfur content in the diesel fuel was reduced to
less than 0.05 %, and the content of aromatic compounds was reduced to less than 20% by volume9 Thus it became possible
to produce Swedish Class 2 fuel.
The aromatics content in diesel fuel can be lowered to the values established by the moderate standards by means of
single-stage hydrotreating over a NiMo catalyst of the TK-525 type. In order to reduce the content of these compounds to the
levels specified by the rigid standards, low-sulfur feedstocks should be subjected to single-stage hydrotreating over a catalyst
based on noble metals (TK-907), and feedstocks with higher sulfur contents should be subjected to two-stage hydrotreating with
a NiMo catalyst of the TK-525 type in the first stage, and TK-908 based on a noble metal in the second stage.
A flow plan for two-stage catalytic hydrotreating is shown in Fig. 3. The process consists of initial hydrotreating,
intermediate treatment, final hydrotreating, and final treatment of the product.

286
 The hydrogen that enters after primary hydrotreating and additional treatment is used in the final stage of the process,
and its pressure is maintained at a l e 'el that will minimize the compressor loading. For this reason, the diesel fuel after the
separator contains a considerable amount of dissolved hydrogen sulfide, which is removed in the intermediate treating section
by stripping with steam or with circulating hydrogen that is passing from the amine treater. The second-stage reactor, charged
with a catalyst based on a noble metal, operates at a somewhat higher pressure than that in the first-stage reactor, so that the
hydrogen after the second stage can be used in the first stage.
Thus, in order to improve the hydrotreating of diesel fuel, Topse is proposing the use of catalysts that it has developed:
a nickel-molybdenum catalyst (TK-525), and a catalyst based on noble metals (TK-907 for low-sulfur feed, and TK-908 for
feeds with sulfur content up to 500 ppm). In addition, this firm is proposing the following process variations in obtaining a
greater degree of catalytic hydrotreating of diesel fuel: a single-stage process with the currently used catalyst replaced by one
of the catalysts they have developed; a single-stage process with the installation of a parallel catalytic reactor and replacement
of the catalyst; and a two-stage process using TK-525 in the first stage and TK-907 or TK-908 in the second stage.
Realization of these technologies may be a major factor in solving ecological problems related to pollution of the
ground layer of air in the operation of automotive vehicles, ships, locomotives, and commercial diesels.

287