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Abstract: The poor quality of crude oil obviously leads to high sulfur contents of oil products, and the technology for
desulfurization of crude oil is urgently needed so that the sulfur contents in petroleum product could be reduced from the
root. This paper describes the progress in technology for desulfurization of crude oil. The present technologies for
desulfurization of crude oil include caustic washing, dry gas desulfurization, hydrodesulfurization (HDS), etc. The new
combined technologies for desulfurization of crude oil being studied are: biodesulfurization (BDS), hydrogenation-
bacterial catalysis, the microwave-catalytic hydrogenation, the BDS-OD-RA desulfurization and oxidative desulfuriza-
tion in electrostatic fields, and the ultrasonic/microwave-catalytic oxidation applied in our lab, with their development
trends being also discussed.
Key words: crude oil; desulfurization; development progress
The poor quality of crude oil currently can obviously re- 2.1 Caustic washing method for oil desulfurization
sult in the high sulfur contents of oil products, which can
Caustic washing method is mainly aimed at removing the
lead to corrosion, catalyst poisoning, environmental pol-
sulfides from the crude oil by using the caustic solution. At
lution and other negative consequences[1-4] (Figure 1)[5].
present, this method is widely used in the oil industry. The
The treatment of high-sulfur crude oil is becoming the fo-
advantage of this method is that the process is simple and
cus of research in China’s oil refining industry[6]. The con-
the cost is lower. But this method contains many defects
ventional equipment cannot deal with the high-sulfur crude
such as the poor quality of oil products and lower effi-
oil during petroleum refining processes. The increasing
ciency of desulfurization. However, this method can’t re-
sulfur content of crude oil also results in an increase in
move all sulfur compounds from the crude oil, especially
sulfur content in automotive gasoline, diesel fuel, and jet
the organic sulfides. At the same time, it brings too much
fuel. To meet the needs for producing clean fuels, decreas-
sulfide-containing wastewater, which greatly pollutes the
ing the sulfur content of crude oil becomes an urgent task.
environment. So, it is urgent to improve this method or find
Studying new desulfurization technology and raising the
a better way to reduce the sulfur contents in petroleum
efficiency of desulfurization processes are the keys to bring-
products.
ing more profits to the oil refining companies[7].
2.2 Dry gas desulfurization method
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December 30, 2010 Liu Lin, et al. Progress in the Technology for Desulfurization of Crude Oil
Firstly, the sulfur compounds are removed from the crude There are two disadvantages associated with this method.
oil; and secondly, after settling treatment and dehydration Firstly, this process is not very efficient. Secondly, one kind
of crude oil, the sulfur compounds are removed again so of bacteria can only remove one or few sulfides[13]. We are
that corrosion of the process equipment and the pipelines now focusing on developing new bacterium, preparing new
will be minimized to secure better working conditions and biocatalysts, improving the capability of the desulfuriza-
avoid accidents. tion technology. The efficiency of biocatalysts and envi-
ronmental adaptability are the important factors in com-
Gas stripping process can reduce significantly the H2S con-
mercialization of the desulfurization technology[14-16]. Other
tent in crude oil. But this method has its disadvantage be-
factors to be assessed include the location of refineries and
cause the efficiency of desulfurization will change with the the biological treatment costs.
water content in the feedstock. Sulfate-reducing bacteria
(SRB) can convert a part of organic sulfides into inorganic According to a report, Iran’s Sharif University of Technol-
sulfides, causing the H2S content to increase in the next ogy has used the bacterial desulfurization process to treat
phase of desulfurization[9]. And the rate for removal of other heavy and sour crude oils in place of the existing refinery
sulfur-containing compounds is very low. desulfurization process. The bacteria can remove 65%—
76% of total sulfur from heavy crude oil extracted from two
2.3 Hydrodesulfurization (HDS) different oilfields, while this desulfurization process is car-
ried out at a temperature below 30 [17-18]
.
Hydrodesulfurization is one of the catalytic desulfuriza-
tion processes, which aims at turning organic sulfur com- The HDS process and the BDS process have different
pounds into H2S using H2 as the reactant in the presence of characteristics, they can complement with each other. Now
metal catalysts operating at high temperature and pressure. some researchers are trying to use both HDS and BDS to-
The resultant hydrogen sulfide is then removed from the gether for processing the high-sulfur crude oils under high
system[10]. This method is widely used in oil industry in pressure and at low space velocity during hydro-upgrading
China since 1955. However, the HDS process features a process. On the other hand, researchers are making strenu-
complicated procedure, high production cost and high ous efforts to manufacture cheaper H2 product, and when
materials consumption. With an increasing ratio of heavy the technology continues its development, it is possible to
crude oil supply to the oil refinery, the sulfur content in combine the two technologies in the near future[19-21].
crude slate is growing, which leads to a shortened catalyst
3 New Combined Technologies for Desulfurization of
life at the refinery. Furthermore, the HDS process needs
Crude Oil
more H2, so the production cost will increase a lot[11].
The currently available desulfurization technologies are
2.4 Biodesulfurization (BDS)
not perfect, and their disadvantages loom more clearly.
BDS is a new bio-catalytic desulfurization method, which The current technologies for desulfurization of crude
has been applied since the 1980s. According to the prin- oil cannot be suited to the market needs obviously. All
ciple of enzyme catalysis for implementing the specific domestic and foreign researchers have been doing a lot
reaction for C—S bonds cleavage performed by micro bio- of effective work to reduce or eliminate the pollution
logical flora, sulfides in crude oil can be turned into el- resulted from processing of sour crude oils. Many new
emental sulfur that can be removed. In the process of combined technologies for desulfurization of crude oil
desulfurization, the sulfur containing pollutants are trans- are being studied, such as the biodesulfurization (BDS)
formed into sulfides and H2S by biological reduction, and process, the hydrogenation-bacterial catalysis method,
the elemental sulfur can be removed via the process of bio- the microwave-catalytic hydrogenation method, the
logical oxidation. Normally we use photosynthetic bacte- BDS-OD-RA desulfurization process, the oxidative des-
ria and colorless sulfur bacteria in the BDS process, and ulfurization in electrostatic fields, and the ultrasonic/
crude oil should stay a few days in the system to be treated microwave-catalytic oxidation method that has been
by the BDS method[12]. applied in our lab.
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China Petroleum Processing and Petrochemical Technology
Leshchev S. M.[22] invented the hydrogenation-bacterial 3.3 BDS-OD-RA three-step integrated desulfurization
catalytic process. This method involves two steps: firstly, process
hydrogenation of the crude oil is carried out in order to
The BDS-OD-RA method is a three-step integrated process.
remove unstable organic sulfides contained in the crude
Desulfurization of high-sulfur crude oil by BDS needs
oil, then an artificial culture of organic sulfur compounds
anaerobic conditions, combined with oxidation and ad-
with selective bacteria named Rhodococcus rhodocrous is
sorptive desulfurization to make this process viable. Des-
used in the desulfurization process. During the biological
ulfurization of low-sulfur crude oil by BDS needs aerobic
oxidation process, organic sulfides (such as dibenzothio-
conditions, combined with oxidation and adsorptive des-
phene series) are subjected to C—S bond cleavage reaction
ulfurization (as shown in Table 2)[25]. So this combined
and turned into inorganic sulfides. Hence this method can
technology for crude oil desulfurization is an important
remove sulfur compounds from oil products efficiently.
development trend.
3.2 Microwave- catalytic hydrogenation process for
desulfurization 3.4 Oxidative desulfurization in electrostatic fields
Microwave energy can be used as the power for regenera- The process of oxidative desulfurization of oil products in
tion of the HDS catalyst. Integrating microwave,catalysis electrostatic fields applied in our lab is carried out as follows.
and hydrogenation together in the desulfurization process During the pretreatment process, the desulfurizer is loaded
is more efficient than the traditional technology of des- into the desalter drum, and the feed oil in an electric field is
ulfurization as shown in Table 1[23]. And microwave in- heated under intensive agitation and mixed with the des-
ducement can improve the effect of chemical desulfuriza- ulfurizing agent to achieve a complete desulfurization of
tion and better desulfurizing results were gained. The des- the oil. Then the sulfides that are removed after desulfur-
ulfurizing efficiencies increased from 18.6%, 21.8%, ization reaction are discharged to the wastewater treatment
28.5% and 24.3% to 34.7%, 33.3%, 34.5% and 43.3%, system[26-27].
3
December 30, 2010 Liu Lin, et al. Progress in the Technology for Desulfurization of Crude Oil
This method is mainly aimed at removing most of mercap- may cause the formation of hydrogen peroxide in the mix-
tans and few thioethers contained in the feed oil. But with ture to react upon sulfides that are then turned into some
increasing boiling points of petroleum fractions, their mer- sulfates, sulfoxides and few sulfones. The solvent can be
captans and disulfides contents drop down immediately, reused after regeneration, while sulfoxides and sulfates can
and the thioethers content grows first, and then falls down, be used to make other products[30-31]. The ultrasonic-oxida-
while the content of thiophenes keeps rising. Most of sul- tive desulfurization process has a lot of advantages such as
fur in crude oil exists in the form of thioethers and simple operation, lower cost, low reaction temperature, low
thiophenes in higher boiling petroleum fractions, these in- operating cost and high efficiency. This technology has a
active sulfur compounds are much more difficult to be re- bright future[32].
moved than active sulfides[27].
Using microwave in combination with the catalytic oxida-
Moreover, some researches are also studying the methods for tive desulfurization is more efficient than a single catalytic
preparation of Sb/Sn intermetallic compound with Al addi- oxidative desulfurization of crude oil as evidenced by the
tion and its behavior for desulfurization of crude oil emulsions. results presented in Table 3.
The desulfurization mechanism was achieved by the electro-
Ultrasonic wave can become a very useful tool in the oil
chemical reaction between sulfides and the Sb/Sn surface un-
desulfurization industry. Ultrasonic wave combined with
der electric current induction in combination with the physi-
other technologies can reduce the temperature, the con-
cal adsorption on active sites like vacancies formed by re-
sumption of power and solvent, the amount of waste dis-
moving Al atoms on the alloy surface[28].
charge and the production cost, which can also increase the
3.5 Desulfurization process involving ultrasonic/ micro- efficiency of recycling and product purity. On the other
wave - catalytic oxidation hand, this process does not cause environmental pollution to
promise a rosy future. This method can fully apply the prin-
The SulphCo Inc. uses the ultrasonic wave to remove the
ciple of cavatition resulted from ultrasonic wave vibrations
sulfur compounds from oil, and large-scale ultrasound tests
are being carried out in the EU. The company’s technology to realize the function of extraction and mechanical agitation,
and the microwave power is applied to improve the pre-des-
can turn the sour heavy oil into light oil with little sulfur
content to produce more useful oil products[29]. ulfurization effect that is applied in our lab currently.
This technology is realized by mixing the feed oil and the 4 Prospects on Development of Crude Oil Desulfurization
water together with a small amount of oxidizing agent and At present, the commercial methods for desulfurization of
catalyst in a container, in which the mixture will react upon petroleum products have their own deficiencies. It is neces-
each other under cavatition effects. In the course of reac- sary to improve the desulfurization process to maximize
tion the feed oil receives the energy from ultrasonic wave the sulfur removal efficiency and turn the waste into trea-
to mix intensively with water, while the temperature will sure that should be reused. The desulfurization efficiency
raise to more than several thousand degrees of centigrade and economic benefits should be compatible, and the ex-
with the pressure increasing to more than 1013.2 MPa, that isting facilities should be fully utilized to provide quick
4
China Petroleum Processing and Petrochemical Technology
5
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