INNOVATIVE REFINING TECHNOLOGY1 – CRUDE OIL QUALITY

IMPROVEMENT (COQI®)

Hanni V. Doctor and H. D. Mustafa*

Real Innovators Group, Chemical Engineering Division, RIG House,
12th Road, Santacruz E, Mumbai 400055, India
*
Corresponding author. Phone: 9122 26187005, Fax: 9122 26187005,
E-mail: hannidoctor@hotmail.com.

Abstract
Crude oil is a dense, dark fluid containing many varieties of complex hydrocarbon molecules, along with organic
impurities containing sulfur, nitrogen, polycyclic aromatics and asphaltenes, heavy metals and metal salts. In this
paper we introduce a novel, stand alone Crude Oil Quality Improvement (COQI®) technology for improving
crude oil used in refineries. The final crude oil obtained from this product is free from 90% impurities. Using this
innovative technology refining costs can be reduced by 25 to 40%.

Keywords: Crude, Sulfur, Impurities, Quality, Refinery.

1. Introduction
Crude oil differs from one another in a large number of chemical and physical properties, many of which play an
important part in their refining and subsequent sale as refined products. It has been known that heavy crude
contains many impurities. Many of the impurities are in concentrated form. Sulfur has been recognized as one of
the major impurity, which affects the quality of the final refined product and processing cost. Moreover there are
certain impurities,which affects properties of crude oil and creates many operational and quality issues. Apart
from affecting the cost of recovery and refining, amount of waste produced is high. Due to high concentration of
these impurities, these crudes are labeled as poor quality crudes and have a lower price in the market. The
conventional methods used in overcoming poor quality crudes are very cumbersome and not cost effective.
Outcome of this study should help in planning future road map to gain better control on crude oil viscosity and
API gravity, broaden the crude refining spectrum, and reduction of sulfur in feedstock to required lower level.

1.1 Technical Facts

World refineries have spent more than $190 billion producing cleaner petroleum and diesel fuels. Indian
refineries, which process more than 2.3 million bpd of crude oil, need to invest $ 8.2 billion (estimate based on
available technologies) by 2010 to meet strict emission rules to reduce pollution (TNN, 2002, p. 26). In many
parts of the world automotive fuels have 0.25% sulfur content, which is being reduced to 0.05% and further
below. Profit margins are very low, hence any technology that takes cost out of refining and production is an
asset. Typically crude is valued based on its yield of Intermediate and finished products (increased quantities)
and on its sulfur content, which is decreased to its lowest in the COQI® technology.

1.2 Major Existing Problems

In crude oil compounds containing only carbon and hydrogen in their molecular structure are desirable because
they are responsible for the high heating value of petroleum. Compounds containing sulfur and nitrogen are not
favorable during combustion because they are converted to sulfur dioxides and nitrogen oxides, which cause acid
rain.

Sulfur in petroleum pollutes the air when oil products burn. Sulfur in gasoline poisons the catalyst in catalytic
converters and causes them to stop working. The sulfur content of crude oils explored is increasing at the rate of
¼ % annually and increased sulfur levels in crude oils increases refining costs. Higher sulfur products leads to

1
Awarded merit prize in NASA sponsored Create The Future design contest in 2004 Ref.
http://techbriefs.com:8080/cached.jsp?idx=0&id=3492
Innovative Refining Technology1 – Crude Oil Quality Improvement (Coqi®) 331

increased emissions of sulfur dioxides and resultant acid rain thus giving poorer performance of vehicle
emissions control systems. Conventional refining processes encounter severe corrosion problems when
appreciable amounts of sulfur and sulfur compounds are present.

Naphthenic acids cause severe corrosion problems when noticeable amounts of organic acids are encountered in
processing of crude oils. Presence of salt water enhances the corrosion problems. Through acid exchange, salty
crude oils, which contain naphthenic acids, may exhibit the severe corrosion characteristics of hydrochloric acid.
Expensive corrosion resistant alloys must be used to construct if we use normal distillation methods.

Waxes distributes throughout refining products depending on its boiling characteristics. Accumulation of wax in
crude oil piping raises pumping expenses and cleaning costs after accumulation on pipe walls.

1.3 Existing Processes

The current technologies in the market for crude oil quality improvement involve
• Upgrading an oil stream containing naphthenic acid and sulfur components: This technology is currently
employed in most crude oil cleaning plants and is highly inefficient and cannot achieve the Euro 3 norms to
be introduced later in 2005, hence will become an obsolete technology (Perin, 2000, p. 10 – 12).
• Special bacterial biocatalyst: Too expensive a technology, at tenfold prices of the COQI® (Premuzic and
Lin, 1999, p. 38 – 39).
• Filter method: Very difficult to implement to existing plants and the quality delivered is half that of the
COQI® technology (Yen, 1998, p. 20)

2. Novel Approach

Refinery crude processing is based on crude with all impurities as input. Step by step it tries to reduce impurities
by changing it to less harmful component or remove after converting to separable component. Processes like
desulfurization, hydrogenation, hydro cracking etc. are used to achieve this. The crude oil cleaning process is
conceptualized on similarities to the efficiency of human digestive system. In similitude of how the human body
rejects unwanted components from food and extracts only useful constituents crude oil cleaning follows the same
rhythm. This process has the potential to revolutionize the oil industry, satisfying the requirements for clean
burning, low sulfur fuels, and reduce the enormous economic pressures on both upstream and downstream oil
processors (Doctor and Mustafa, 2003, p. 62 – 64). Most of the reserves of major oil companies consist of
challenging crude oils with high levels of impurities. Crude oil cleaning is a novel stand-alone process that can
be deployed at the oil production or terminal site to avoid the price penalty for high sulfur crude transport and
substantially reduce the refinery’s economic burden for desulfurizing higher sulfur crude. Overall the crude oil
cleaning process is cost beneficial because the sulfur content of oil put in the pipelines is taxed and there is much
interest in removing that sulfur before it enters the pipeline.

Figure 1: Overall Process Summary of COQI® Technology and Initial results of the COQI® technology
processed on DURI Crude
332 Advances in Energy Research (AER – 2006)

2.1 Simulations and Experimental Study of Heavy Crude Oil

COQI® technology was applied on Duri heavy crude oil to improve quality and explore economic advantage.
Major quality parameters targeted were sulfur, API gravity and viscosity.

2.2 Goal of the Study

To check the feasibility of upgrading Duri crude using COQI® technology and check the feasibility of improving
refinery throughput, quality and yield. To achieve above goal, a study supported by preliminary simulation and
experimentation is carried out to check feasibility of improving crude oil viscosity, API gravity, reduction /
removal of sulfur, increase crude distillation yield and overcome other operational problems.

2.3 Approaches for Upgradation of Heavy Crude Oil

The following major approaches were incorporated for the targeted partial crude oil upgrading using COQI®
technology:
• Hydrogen is not required to achieve the project objectives of separating / removing sulfur and metal
impurities. Impurities are treated after it is separated from the crude.
• No chemical reaction is carried out for separation of impurities. Impurities are treated either selectively or
separately and thus the desired hydrocarbon quality is not affected.
• Separation processes are carried out below 100oC temperature to ensure no change in overall composition of
crude oil and thus not effecting crude oil hydrocarbon quality and distribution.
• Focus on viscosity reduction (increase in API gravity by points) to meet crude oil handling and
transportation requirements, increasing throughput and reducing pumping and handling costs.
• Develop a heavy oil upgrading system that has low capital cost requirements, has minimal controls, and is
easy to operate.

2.4 Major Quality Components in Duri Crude

Implementing the COQI® technology can guarantee the reduction in impurities and improving the quality of
heavy crude oil. The guaranteed and targeted parameters based on simulation and experimental analysis are
listed in Table 1:

Table 1: Results of processing DURI crude by COQI® technology

Sl.No Characteristics DURI Quality parameters after Test Method

UOM CRUDE processing through COQI®
technology
1 Specific gravity @ 15.56 0.9317 0.86 D 5002
0
C
2 API gravity °API 20.4 33 (+/- 2) D 287
3 Viscosity @ 50 °C cSt 419.2 35 D 445
4 Viscosity @ 71.1 °C 75.2 5.1 D 445

5 Sulphur Wt.% 0.203 0.05 D 4294

6 Average Molecular wt. 500 350 BHP Method 31

7 Refinery through-put % 100 (Base) 165 to 170

Improvement
Innovative Refining Technology1 – Crude Oil Quality Improvement (Coqi®) 333

Table 2: Results of processing RATAWI heavy crude by COQI® technology

Sl.No Quality parameters after Test Method

Characteristics UOM Ratawi Crude processing through COQI®
technology
1 API gravity °API 24.5 36.2 D 287
2 WT D 4294
Sulfur 3.88 0.56
%
3 Kinematics Viscosity at D 445
cSt 30.7 4.56
38 °C
4 Vanadium ppm 47 2 D 5863
5 Pour Point °C -23 - 32 D 97
6 WT D 3279
Asphaltenes 6.1 0.3
%
7 Average Molecular wt. 320 295 BHP Method 31

2.5 Promising Envisaged Improvement

Our preliminary study and simulation shows:
• Significant viscosity reduction envisaged. 85 to 90 % reduction in cSt values.
• Improvement in API gravity by 10 to 12 units.
• Significant sulfur reduction. Average 75 % of selective sulfur removal by weight achieved.
• Specific gravity reduction achieved by 0.07 from 0.09 units.
• Average molecular weight improved by 50 to 150 units.
• Expected improvement in refinery throughput by 65 to 70%.

3. Discussion of Simulations and Experimental Results

3.1 Viscosity
Viscosity reduction is achieved by removing impurities that contributes to higher viscosity. Higher viscosity is
contributed in Duri crude by higher molecular weight molecules, which includes polycyclic aromatics including
asphaltenes and other compounds with higher molecular weight like maltenes. These molecules form emulsion
with hydrocarbons in crude resulting in very high viscosity. COQI® selectively rejects these impurities by
breaking emulsion without using any additives. This improves viscosity drastically.

Aromatic impurities which are very tough to remove is rejected by COQI® using selected process conditions and
intermittent solvents. COQI® designed process based on affinity separation helps in better understanding of
chemical changes in crude oil and viscosity improvement.

Reduced viscosity enables more rapid and uniform feedstock management, improved heat transfer, faster mixing
and shorter residence time ensuring consistent quality. Viscosity is reduced from 419.2 cSt to 35 cSt at 50oC in
DURI crude, while in RATAWI crude viscosity is reduced from 30.7 to 4.56.

3.2 API Gravity

API gravity is the most frequently used measure to estimate the quality of a crude oil. It is one of the parameters
focused for determining the price of crude oil. Generally, heavy crude oils have API gravity of 20 or less and
light crude oils measure 34 or more units. Heavy crudes produce lower quantities of light and middle distillates
334 Advances in Energy Research (AER – 2006)

and higher quantities of residue. Global demand patterns are moving towards an increasing requirement for light
and middle distillate products.

Envisaged Improvement in API gravity in Duri crude is from 20 to 33, i.e. improvement of 13 unit points while
in Ratawi crude, improvement of 11.7 units observed.

COQI® technology attacks the route cause for the lower API gravity, remove very high molecular weight
particles from crude oil by breaking emulsion, removing impurities and thus shifting average molecular weight
to lower side. In general terms, the thickness of oil is reduced and fluidity is increased.

3.3 Sulfur
High sulphur crudes are likely to fall in value relative to lower sulphur crudes as product sulphur specifications
fall further. However, the majority of known remaining crude reserves are having high sulphur. Sulfur is the
other parameter focused for determining the price of crude oil and determining factor in refinery processing cost,
apart from additional infrastructure cost.

Simulation and initial study gives confidence of reducing sulfur by average 75 % by weight. COQI® technology
removes sulfur with complex molecules selectively from crude oil. These are normally high boiling sulfur
compounds, i.e. boiling at 565oC and ends up partly in residue and gas oils. Lower boiling sulfur compounds are
separated and treated. COQI® technology incorporates complex alteration of sulfur compounds and separates
sulfur from crude mainly in gaseous form. This makes removal of sulfur easy and disposal in traditional refinery
way.

3.4 Conclusion Derived from Simulations and Experimental Results

Very selective impurity removal can be targeted using COQI® technology. Apart from improvement in quality
and cost, other benefits envisaged are
• Increase in through put up to 65 to 70 % as viscosity of the crude can be reduced drastically.
• Increase in plant uptime as majority of impurities contributing to fouling of exchangers, burners, etc are
removed or reduced.
• There is ample scope of producing higher value byproducts like paraffin oils.
• About 10 % increase in yield will change the bottom line for refineries using COQI® technology. Residue
after vacuum distillation or atmospheric distillation reduces by 50 % minimum.
• Improvement in transportation efficiency reduces power consumption and thus cost.

3.5 Budgetary Capital Cost for Implementing the COQI® Technology

Capital cost for the process plant based on COQI® technology for removing sulfur and other impurities from
crude oil and increasing refinery through-put by 70 % is just 15 % of the cost of new refinery with same benefits.
With additional 10% of the cost of new refinery, one can add process plant for increasing yield by 10%.
Operating cost of COQI® process is envisaged to be US $ 1.2 to 1.5 per barrel. Above analysis was based on
DURI heavy crude oil but process is applicable for all types of crudes. Technology is applicable for improving
all types of crudes. Compared to present per barrel per year refinery capital cost, COQI® technology is very
competitive and cost effective. 3.5

3.6 Competitive Advantages

The innovative crude oil cleaning project has enabled to achieve the standards to be reached by regular
traditional approaches in 2010 by 2006, hence providing a head start of more than 4 years to the oil refining
industries. World refineries that need to invest $ 190 Billion in crude oil cleaning by completely modifying their
manufacturing and cleaning process, now have an innovative stand alone project at their hands, which can be
used along with their existing plants thus saving them billions of dollars and achieving pentagonal benefits over
the existing traditional processes. Price saving using COQI® is around 25 to 40%. Due to the stand-alone nature
of the process it can promote development of outsourcing plants, all around the world, which can benefit the
global economy. Crude oil quality improvement has enabled the cost-effective recovery of even the heaviest
crude which makes up over 60% of the world's known oil reserves but which are now trapped below the surface
Innovative Refining Technology1 – Crude Oil Quality Improvement (Coqi®) 335

and are difficult and costly to recover. Cleaning of crude oil doubles the capacity of refining in existing
refineries.
4. Conclusion
The COQI® approach looks beyond the short term to meet the long-term strategic needs of the world energy. Oil
resources once deemed out of practical reach can be made available for processing so that the resulting fuels
burn cleanly. Once crude has been produced, this process can act as a desirable refinery pre-treatment, removing
much of the sulphur, nitrogen, wax and metals. Besides enhancing the overall efficiency of the refining process,
this action has a positive impact on factors that can contribute to global climate change, reducing green house

References
1. Doctor V.H., H. D. Mustafa, 2003, Crude Oil Cleaning with Solvent, Hydrocarbon Asia, 1, 62 – 64.
2. Premuzic E., M. Lin, 1999, Biochemical upgrading of oils, Discover Brookhaven, 4, 38 – 39.
3. Perin M., 2000, Energy Beat, Houston Business Journal, 12, 10 – 12.
4. TNN, 2002, Indian Petroleum Minister in Parliament, The Times of India, 11, 26.
5. Yen T. F., 1998, Smart Filter Promises Worldwide Applications: Nanotech Device Remove Sulfur, Refines
Crude, Science Daily, 6, 20.