Koya University
Faculty of Engineering
Chemical Engineering Department – 2nd stage
Petroleum and Gas Properties
Non-hydrocarbon Components in Crude Oil
Instructor
Mr. Ribwar Krmanj Abdulrahman
Prepared by
Safeen Yaseen Jafar
Submitted Date
24 Nov 2020
Table of Contents
Introduction........................................................................................................................................................................ 1
Literature Review .............................................................................................................................................................. 2
Discussion .......................................................................................................................................................................... 7
Conclusion ......................................................................................................................................................................... 7
Reference ........................................................................................................................................................................... 8
Introduction
In organic chemistry we have hydrocarbons, non-hydrocarbons, organo-metallic compounds and
other components in crude oils. Also, these compounds or components exist in all crude oils or petroleum by
tiny amounts.
So, Non-hydrocarbons found in crude oil and petroleum products may be small in quantity, but some of them
have a major effect on the consistency of the commodity. They have noxious or harmful effects in certain
situations, and must be extracted or converted during the processing process to less harmful compounds.
Sulphur, nitrogen, and oxygen are the most common occurring non-hydrocarbons. Tiny quantities of
vanadium, nickel, sodium, and potassium may also be present.[1]
There are different sources of non-hydrocarbon compounds in crude oils. And streams of refineries. The
organic compounds of sulfur, nitrogen, and oxygen are the most common. The analysis of the nonhydrocarbon components of petroleum is related to the petroleum industry 's issues, such as the deterioration
of refining units, the poisoning of important catalysts during the upgrading of petroleum products and the
manufacture of environmentally suitable fuels. In addition to these adverse consequences, non-hydrocarbons
play a major role in geochemical studies of petroleum. [2]. In addition to the practically infinite mixtures of
hydrocarbon compounds that form crude oil, sulfur, nitrogen, and oxygen are usually present in small but
often important quantities. Sulfur is the third most abundant atomic constituent of crude oils. It is present in
the medium and heavy fractions of crude oils. In the low and medium molecular ranges, sulfur is associated
only with carbon and hydrogen, while in the heavier fractions it is frequently incorporated in the large
polycyclic molecules that also contain nitrogen and oxygen. [3]
Inclusion of organic compounds of nitrogen, oxygen, and sulfur serves only to present crude oil as an
even more complex mixture than was originally conceived. Nevertheless, considerable progress has been
made in the isolation and/or identification of the lower-molecular-weight hydrocarbons, as well as accurate
estimations of the overall proportions of the hydrocarbon types present in petroleum. Indeed, it has been
established that as the boiling point of the petroleum fraction increases, not only the number of the
constituents but the molecular complexity of the constituents also increases. Crude oils contain appreciable
amounts of organic nonhydrocarbon constituents, mainly sulfur-, nitrogen-, and oxygen-containing
compounds and, in smaller amounts, organometallic compounds in solution and inorganic salts in colloidal
suspension. These constituents appear throughout the entire boiling range of the crude oil but tend to
concentrate mainly in the heavier fractions and in the nonvolatile residues. [4]
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Literature Review
Non-Hydrocarbon Component Types
We have many of non-hydrocarbon compounds that have bad effects on crude oil and our
environment even our body and equipments/devices in industry, oil and gas companies. These nonhydrocarbons also have economic losses on countries. So, the most common occurring non-hydrocarbons are
Sulfur, nitrogen, and oxygen. There may also be small amounts of vanadium, nickel, sodium, and potassium.
Some disadvantages of these compounds
1. Harmful effects on equipments for example Corrosion, like corrosive of pipeline while transporting
crude oil in pipeline or any equipments.
2. Environmental Bad effects like pollution.
3. Bodies Injury.
So, we focus on some components (Nitrogen, Water, Oxygen, Sulfur, Metallic, Porphyrin contents, etc...),
their effects and solve for them.
1. Nitrogen Components
In crude oils, organic nitrogen compounds occur either in a basic heterocyclic form such as pyridine
(C5H5N) and pyrrole (C4H5N) or as porphyrin in a complex structure. The nitrogen content is very low in
most crudes and does not exceed 0.1 percent wt. The nitrogen content can reach up to 0.9 percent in some
heavy crudes, however. Compounds of nitrogen are more thermally stable than compounds of sulfur and are
therefore concentrated in heavier petroleum fractions and residues. Light streams of petroleum may contain
trace amounts of nitrogen compounds, which should be eliminated because many processing catalysts are
poisoned. [5]
Basic Nitrogen VS Non-basic nitrogen
Basic nitrogen compounds are mainly those having a pyridine ring, and the non-basic compounds have a
pyrrole structure. Both pyridine and pyrrole are stable compounds due to their aromatic nature. [6]
Nitrogen Component Disadvantages in Crude Oil
Nitrogen need to be removed from crude oil because Nitrogen impurities in hydrocarbon fuels have a severe
environmental impact resulting from the contribution nitrogen oxides (produced during combustion) (PDC)
to acid rain; Nitrogen impurities are effective catalyst poisons that slow down the processing of crude oil.
Remove Nitrogen from Crude Oil (Nitrogen Extraction from Crude Oil)
During hydrotreatment of petroleum fractions, nitrogen compounds are hydrodenitrogenated to ammonia
and the corresponding hydrocarbon. For example, pyridine is denitrogenated to ammonia and pentane:
Figure (1) Pyridine is denitrogenated to Ammonia and Pentane
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Figure (2) Above diagram shows the extraction of the nitrogen from crude oil by hydrodenitrogenation.
2. Water content in crude oil and its disadvantages
Various quantities of water and sediment are found in crude oil. Crude oil must not contain more than 0.5
to 1 percent of water because water will induce corrosion during the refining process. It is therefore crucial to
know precisely the remaining amount of crude oil in the water after its production. [7]
Remove water from crude oil
Heating crude oil for sand and water removal. Using SRA Plate & Shell Heat Exchanger or SP Pillow
Plate heat exchangers in treater tanks to extract the sand and isolate created water, emulsions of viscous
crude, water and sand are heated with steam or glycol. [8]
Figure (3) In this process above you can see the water treatment.
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3. Sulfur Components
The amount of total sulfur (in all its forms found in crude oil is basically determined by measuring the
unity of the SO produced by the combustion of the crude sample, and the effect is taken into account when
the price of crude oil is calculated. Elementary sulfur and dissolved HS may also be measured where they are
present. Chemical sulfur compounds, dissolved hydrogen sulfide and often even suspended sulfur are present
in crude oils. Generally speaking, a crude's average sulfur content is between 0.05 and 5% by weight. Ratios
that are compatible with organic products that are known to be the sources of crude oil. [9]
Figure (4) and (5)
These figures show us H2S and C4H4S
The sulfur compounds are classed in six chemical groups.
o
o
o
o
o
o
Free Elemental Sulfur (S).
Hydrogen Sulfide (H2S).
The Thiols.
The Sulfides.
The Disulfides.
Thiophene and Derivatives.
Disadvantages of Sulfur Components
Sulfur is a compound with many industrial applications and as it is present in the amino acids of
many proteins, is also important for all living beings. However, it's certainly an unwelcome presence in the
refining phase of crude oil and needs to be eliminated for two reasons. First, when oxygen and water vapor
combine with the sulfur dioxide arising from gasoline emissions, becoming sulfuric acid and producing acid
rain. In addition, sulfur can degrade noble metals even in very small amounts in the catalytic reforming
process, which is used to increase the octane quality of petrol. [10]
Summary of disadvantages of Sulfur Compounds
1. Corrosion.
2. Kill Operator Man in a few minutes.
3. Pollution of Environment.
Remove Sulfur from crude oil
The chemical process of extracting sulfur from the hydrocarbon compounds (Hydrodesulfurization)
comprising petroleum products is hydrodesulfurization. This is normally done by a catalyzed hydrogen
reaction at moderate to high temperatures and pressure, such as in the processes of hydrotreatment and
hydrocracking, for example. In refineries, combinations of both methods are used. Around catalysts. [11]
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Figure (6) above diagram shows the extraction of the sulfur from crude oil by hydrodesulfurization. In this
process hydrogen sulfide is produced and the corresponding hydrocarbon released.
4. Metallic Components, their disadvantages on crude oil
The metal content of crude oils, considering their comparatively low concentrations, can range from a
few parts per million to over 1000 ppm, and is of significant importance. Minute concentrations of any of
these metals (nickel, vanadium, and copper) may have a significant effect on catalyst operation, resulting in a
lower distribution value of the component. For example, vanadium concentrations above 2 ppm in fuel oils
can lead to severe corrosion to turbine blades and deterioration of refractory furnace linings and stacks
Distillation concentrates the metallic constituents of crude in the residues, but some of the organometallic
compounds are actually volatilized at refinery distillation temperatures and appear in the higher-boiling
distillates. The metallic content may be reduced by solvent extraction with propane or similar solvents as the
organometallic compounds are precipitated with the asphaltenes and resins. [12]
Remove Heavy Metals from crude oil
We can Remove the heavy oils from crude oil by solvent extraction processes. So, we can see diagram in the
next page to understand more.
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Figure (7) a. Whole process and b. Solvent extraction procedure.
5. Salt Components in crude oil
Salts in crude oil are primarily in the form of chlorides of magnesium, calcium, and sodium, the most
abundant being sodium chloride. These salts are present in two forms: dissolved in crude oil in emulsified
water droplets, as an emulsion of water-in-oil, or crystallized and suspended solids. In downstream
processes, the negative effect of these salts can be described as follows: the formation of salt deposits as
scales where water-to-steam phase change takes place and hydrochloric acid formation corrosion.
Hydrochloric acid is formed at high temperatures by the decomposition of magnesium and calcium chloride.
[12]
Remove the salt from crude oils
Figure (8) in this diagram we can see the remove of salt from crude oil
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Discussion
As we talked along this essay about non-hydrocarbons in crude oil/petroleum. We explained the nonhydrocarbon disadvantages in crude oil or petroleum generally, also we know the one of the crude oil’s
classification is geographic location so the crude oils have different non-hydrocarbon ratio or elements of
them because of composites and constitution of their place. Also, we have to know the crude oil consist of
many of hydrocarbons and tiny amounts of non-hydrocarbons, so their ratio between each other change too.
Sometimes depend on this classification of geographic location foes not true. Because of the length between
them is small. Notice the nitrogen and sulfur which have very disadvantages because of their harmful effects
like corrosive, environmental pollution and other phenomena in the world.
Also, in this essay we have reached that the most common non-hydrocarbons are sulfur, nitrogen, and
oxygen. There may also be small amounts of vanadium, nickel, sodium, and potassium. So, NonHydrocarbons that occur in crude oils and petroleum products may be small in quantity but some of them
have considerable influence on product quality. In many cases they have noxious or harmful effects and must
be removed or converted to less harmful compounds during the refining process
Conclusion
We can conclude this essay in here by reviewing some in information in this essay and rearranging
the facts and explain the result of this essay. So, we know the crude oil is the hydrocarbons as main and has
trace of non-hydrocarbon in it. Also, we must be separate the non-hydrocarbons from crude oils because of
their disadvantages and harmful of them. At first, we focused on information about the non-hydrocarbons
and its composition in crude oils, as knew all crude oil types depend on the non-hydrocarbons that involved
in it.
We can summarize this essay in this point below:
1.
2.
3.
4.
5.
Non-hydrocarbons exist in many of crude oils by tiny amounts.
Non-hydrocarbons have a harmful effect on crude oils or any product of petroleum,
All crude oil types depend on the hydrocarbon and Non-hydrocarbon compositions.
We must be removing all Non-hydrocarbons in crude oil by treatment of components.
Also, the Non-hydrocarbons have useful after separate from the crude oils.
Also, we talked about these non-hydrocarbon components in crude oil and their effects, problems or
disadvantages and their solution or extraction from them. In finally, we must be saying that this essay helped
us to reviewing and restudying about this branch of petroleum/chemical engineering.
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Reference
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16 Nov. 2020].
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https://www.mt.com/ch/de/home/supportive_content/ana_chem_applications/titration/M772.html#:~:
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Technology Co., Ltd. [online] Available at: http://www.sehenstar.com/Showsolutions/?16-1.html
[Accessed 19 Nov. 2020].
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[Accessed 16 Nov. 2020].
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Available at: https://www.cividac.com/news/sulfur-a-fundamental-compound-in-nature-to-beremoved-from-crude-oil.html [Accessed 16 Nov. 2020].
11. Nour Shafik El-Gendy, James G. Speight 2015. Handbook of Refinery Desulfurization. [Ebook] 492,
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Desalting Process. Advances in Petrochemicals. [online] Available at:
https://www.intechopen.com/books/advances-in-petrochemicals/crude-oil-desalting-process
[Accessed 16 Nov. 2020].
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2020].
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