DEPARTMENT OF CHEMICAL ENGINEERING

SCHOOL OF ENGINEERING

UNIVERSITY OF PETROLEUM & ENERGY STUDIES

December-2019

Study of Nano-composite based Pour Point Depressant for Waxy Crude oil

Submitted by
ROHIT ARORA, R820217138 (500060316)
YASH CHAUDHARY, R820217134 (500060817)
YASH GUPTA, R820217135 (500061106)
YASH SANGWAN, R820217136 (500061054)
SHIVALI DWIVEDI, R820217105 (500061666)

in

Dr. Upendra Singh Yadav Mrs. Rose Havilah Pulla

Department of Petroleum and Earth Sciences Department of Chemical Engineering
 DECLARATION BY THE SCHOLAR

I hereby declare that this submission is my own and that, to the best of my knowledge and belief,
it contains no material previously published or written by another person nor material which has
been accepted for the award of any other Degree or Diploma of the University or other Institute
of Higher learning, except where due acknowledgement has been made in text.

AUTHOR’S NAME:

ROHIT ARORA (500060316)

YASH CHAUDHARY (500060817)
YASH GUPTA(500061106)
YASH SANGWAN(500061054)
SHIVALI DWIVEDI (500061666)
 CERTIFICATION

This is to certify that the project titled Study of Nano-Composite Based Pour Point
Depressant for Waxy Crude oil, submitted by ROHIT ARORA (500060316); YASH
CHAUDHARY (500060817); YASH GUPTA (500061106); YASH SANGWAN (500061054);
SHIVALI DWIVEDI (500061666) to the University of Petroleum & Energy Studies, for the
award of the degree of BACHELOR OF TECHNOLOGY in Applied Petroleum Engineering. It
is a Bonafide record of project work carried out by him/her/them under my/our supervision and
guidance. The content of the project, in full or parts have not been submitted to any other
Institute or University for the award of any other degree or diploma.

(Signature of Mentor) (Signature of Co-mentor)

Dr. Upendra Singh Yadav Mrs. Rose Havilah Pulla
Department of Petroleum Department of
and Earth Sciences Chemical Engineering

Dated: 16th December 2019

 ACKNOLEDGEMENT

This project would not have been successful without our mentor, Dr. Upendra Singh Yadav
and our co-mentor Mrs. Rose Havilah Pulla, who gave us an opportunity to do this work. We
wish to express our gratitude for his abundantly helpful and offered invaluable assistance,
support and guidance throughout the study.
We would also like to thank Mr. Rahul Kumar, our activity coordinator who provided
resources and plans that help us in our Minor Project, Dr. P. Vijay, Head of the Department of
Chemical Engineering who provided us with an opportunity to develop the project.
We would also like to thank Mr. Anil Kumar who provided us help whenever needed and
helped in providing resources.
We would also like to thank Mrs. Chandra Prabha Verma From The Reservoir Department
Of ONGC, Dehradun.
We would like to thank all those without whose support this project could not have been a
successful one.
 ABSTRACT

In the pipeline industries, precipitation of wax crystals in crude oil has been presenting a costly
problem in the transportation and storage of crude oil. It complicates the low-temperature
properties of oil and pipeline could become completely clogged. A well-recognized and efficient
solution to these problems is Pour Point Depressant (PPDs). However, conventional PPDs (like
POA, EVA) still have some disadvantages, such as unsatisfactory performance, could be affected
by components of oil like asphaltene and have poor thermal resistibility.

Due to the effective advantages of polymer / inorganic nanocomposites, we developed

nanocomposites PPDs by dispersing nanoparticles into polymeric PPD matrices to improve the
performance of conventional PPDs. So, the use of nanocomposites as a pour point depressant for
crude oil has opened the door for the new field of research in the petroleum industry, and it is
very crucial to enhance the efficiency of a nanocomposite as a pour point depressant (PPD) to
modify the waxy crude oil.

In this present work, considering the Indian waxy crude oil as the model oil and synthesize the
partially hydrolyzed Polyacrylamide (PHPA) / Carbon Black as the nano-composite and
thereafter, evaluated the performance of this newly synthesized Nano- composite Pour point
depressant. Characterization of various phuysicochemical and rheological properties through
various instruments like Fourier-transform infrared spectroscopy) (FTIR), Gas Chromatography
(GC-MS) and rheometer. And after performing experiment it is shown that the reduction in
viscosity has been done considerably from 158 cp to 36 cp at a shear rate of 21s-1
 TABLE OF CONTENT

CERTIFICATE

ACKNOLEDGEMENTS

ABSTRACT

INTRODUCTION

LITERATURE REVIEW

MATERIALS AND METHODOLOGY

MATERIALS USED IN THE PROJECT:

METHODOLOGY

RESULTS AND DISCUSSION

CONCLUSION

REFERENCES
 CHAPTER - 1

INTRODUCTION

Crude oil is an important fossil fuel, which contains saturated hydrocarbons, paraffins, aromatics,
asphaltenes, and resins, and has a complex nature. [1] Generally, paraffins are dissolved with a
balanced state in the crude oil at higher temperature,[2] but when the temperature falls below a
certain temperature, i.e., Wax Appearance Temperature(WAT),paraffins with Carbon number
C16-C40 will precipitate out and form a three-dimensional network structure thus, formed the
crystallized wax.[3,4]

Pour point depressants don't bring down the temperature at which wax precious stones start to
frame, called the cloud point or the measure of wax that is shaped—pour point depressants work
by adjusting the gem shape and size, which represses parallel gem growth. There are two known
strategies by which this might be accomplished: surface adsorption and co-crystallization.
Any decrease in an oil's pour point relies upon both the synthesis and properties of the oil, just as
the kind of pour point depressant utilized. Different elements are the substance's relative atomic
weight, its compound piece, and the substance's fixation in the oil. On the off chance that the
centralization of pour point depressant is excessively high, there might be an unmistakable
impact on thickness at higher temperatures

These Wax crystals crystallize in orthorhombic structures and appear as plates.[5] Wax crystals
cause the transition of crude oil from sol to gel. Due to the London forces which are operated
between the wax crystals and large aspect ratio of the plates, a small amount of the precipitated
wax crystals (as little as 0.5 wt.%) could form the volume spanning networks which trapped the
crude oil resulting in high pour point (PP), high yield stress, and a non-Newtonian flow behavior
of the crude oil. [6, 7] This deteriorates the rheological properties and flowability of crude oil,
generating issues in pipeline transportation and storage. The sol-gel transition of crude oil is
denoted by Gelation point (GP).[8]
The GP, at which the elastic modulus of the oil begins to become larger than the viscous
modulus of the oil. This phenomenon of wax deposition reduces the effective diameter of
pipeline and also cause blockage of pipelines under severe low temperature conditions.[9]
Therefore, management of wax precipitation, wax gelation in flow assurance of crude oil and
emergency intervention planning can be a large challenge.[10]Common way of improving the
rheology of crude oil is using traditional Polymeric Pour Point Depressant(PPD). These are
homo and co-polymers of different monomers which can interact with the crude oil through
nucleation, adsorption, and co-crystallization mechanisms. [11] In the Pipeline industries, Comb-
like copolymer and EVA-type polymers which exhibit Pour Point Depressant Properties had
been widely used.[12,13] These two types of polymeric PPDs often contains nonpolar carbon
chains and polar groups, the nonpolar parts could take part in the precipitation process of wax
crystal through nucleation and co-crystallization effects, whereas the polar groups can increase
the repulsion effect for the deposition of wax crystals and interfere in the growth of wax
crystals.[14]

The most effective comb-like PPD for waxy crude oil is PHPA, which co-precipitates with wax
molecules and forms island defects on the wax crystals surface, result in blocking the growth of
crystals.[15,16]These PPDs prevents the growth of wax crystal and modifying the morphology of
wax crystal. However, traditional PPDs also exhibit several drawbacks that limit its application,
including reduction in robustness under the effect of shearing and/or heating.[17] Instead of
crude oil, wax also exists in various polar substances. Asphaltene can influence the viscosity and
pourpoint of oil. Moreover, they can also decrease the efficiency of PPD. Thus, a certain type of
polymer PPD has lack in universality among different oils. [18]

In simple words, it is the coating or adsorption of organic polymer on the surface of inorgonica
nanoparticles. After inorganic nanoparticles were dispersed into the polymer matrix, resultant
properties (such as mechanical, thermal, and electrical) of polymer are improved greatly as
compared to the neat PPDs. The performance of the Nano-composite depends on the
compatibility between the inorganic nanoparticles and organic polymer or by improving the
preparation method. Compared with solvent blending method, Melt Blending method with the
aid of an extruder is a more efficient method in terms of dispersing nanoparticles in the polymer
matrix.Thus, we can enhance its performance by prepared it by Melt Blending method results in
strengthen the adhesion of POA on non-silica and improved stability of material.
 CHAPTER - 2

BACKGROUND

At present, Nano-composite pour point depressants are mainly divided into two types-

a) Blended Nano-Composite Pour Point Depressant

The blended Nano-composite pour point depressant is generally prepared by traditional poly -
octadecyl acrylate(POA) pour point depressant and EVA pour point depressant with inorganic
Nano particles in a certain proportion through solution blending or meltblending.Organic
Modification of inorganic Nanoparticle is another important means to improve the stability of
blended Nano composite PPD which can enhances the compatibility between Nano-particles and
polymer matrix. This is done by chemical grafting, cation exchange and intercalation of organic
molecules.
In 2016, Y. Wang used an ion exchange reaction to organically modify montmorillonite (MMT),
and prepared the Nano-composite pour point depressant (NPPD) by melt blending. They found
that NPPD has good stability in the oil phase the large electrostatic repulsion inhibits the
aggregation of wax particles, and stabilizes the oil system.[20]
b) Polymeric Nano-Composite Pour Point Depressant
Al-Sabagh et al. introduced a polymerizable organic group on the Nano-MMT by ion exchange
reaction, and then used methyl methacrylate (MMA) to prepared the PMMA/MMT Nano-
composite pour point depressant by in-situ radical polymerization which have high compatibility
in the oil.[21] (Figure 1)
 CHAPTER - 2

LITERATURE REVIEW

Literature review was carried out and information related to various problems involved during
the transportation of Indian heavy and waxy crude oils will be collected for different oil fields of
India. After then, heavy and waxy crude oil samples will be collected from the different Indian
oil fields. These crude oil samples will be characterized by different standard ASTM/API
methods and by using different analytical equipment's like High temperature gas
chromatography (HT-GC), Fourier transform infrared spectroscopy (FTIR) TGA/. DTA, and
DSC etc.

Rheological properties of oil samples will be investigated using a rheometer. Then Nano particle
based suitable (emulsifiers), pour point depressants (PPDs) and other requisite additives will be
identified and synthesized in the laboratory. These synthesized nanocomposites /additives will be
characterized on the basis of their physio chemical properties and by using analytical instrument
like FT-IR. Application of synthesized nano-composites will be evaluated as surfactants and
pour point depressants to improve flow ability of Indian heavy and waxy crude oils, respectively,
through pipelines.

The pour point and rheological parameters of the prepared heavy crude oil emulsions and treated
waxy crude oils will be studied using pour point apparatus and rheometer, respectively. Stability
of prepared emulsions will also be investigated using bottle test method. Further, the different
factors such as Surfactant concentration, oil-water ratio, water salinity, pH etc. which affect the
flow behavior of emulsions as well as emulsion stability will be studied thoroughly. For waxy
crude oils, dosage of pour point depressants will also be optimized. A particle size analyzer will
be used to study the droplet size of oil in prepared oil-in-water emulsions. An optical Rao scope
will be utilized to study the changes in the size of wax crystals in waxy crude oil after treatment
with PPDs. Based on the results observed, scientific articles will be written and published.
The influence of the nano-hybrid pour point depressant (NPPD) on flow properties of waxy
crude oil was studied. Rheological results showed that NPPD demonstrated better improvement
in viscosity, yield stress and pour point reduction for crude oil than the conventional polymer
PPD (N6) did Moreover, the viscoelastic behavior data showed that the NPPD doped oil had a
weaker gel network structure at a low temperature compared with N6 doped oil. Differential
scanning calorimetry results revealed that NPPD reduced the wax appearance temperature
(WAT) and the wax precipitation amount within the temperature range from WAT to 20 C. The
difference of shape and size of wax crystals in undoped and doped oils was studied by X-ray
diffraction and polarized optical microscopy. The total interaction energy between wax particles
was calculated according to the Derjaguin– Landau–Verwey–Overbee theory using f potential. It
was found that the energy barrier between the wax particles in the NPPD doped oil was higher
than that in N6 doped oil. The larger electrostatic repulsion inhibited the aggregation of the wax
particles and stabilized the NPPD doped oil system.

The nano-hybrid pour point depressant (NPPD) was used to improve the flowability of the waxy
crude oil. The influence of NPPD on the shape and size of the wax crystals was studied. At the
dosage of 100 ppm, NPPD greatly decreased the pour point, viscosity and yield stress, and it had
a much better improvement of oil flowability than the polymer PPD N6.Time sweep
measurements showed that WCO-NPPD possessed a weaker wax structure than WCO and
WCO-N6 leading to the lower viscosity and yield stress. DSC results showed that NPPD could
reduce the WAT and wax precipitation amount of the crude oil. NPPD performed as
heterogeneous nucleation sites for the paraffin chains and refined the wax crystal particles.

The XRD and POM results confirmed that the crystal shape and size was modified by NPPD.
The wax crystals became more compact and more liquid contents were released from gel
networks. The action mechanism of NPPD was complicated, which might be the combination of
the effects of the nanoparticles and EVA.As the different crude oil or model was adopted in each
study, it was difficult to get the unified theory to explain the experiment results.
Cunzhe He, Yanfen Ding, Juan Chen, Feng Wang, Chong Gao, Shimin Zhang, Mingshu Yang in
2019 has studied the influence of nano-hybrid por point depressant on flow properties of waxy
crude oil. Results showed that NPPD demonstrated better improvement in viscosity (reduction
was done about 82%), yield point stress and pour point reduction of crude oil (from 30.0 degree
Celsius to 3degree Celsius) using the required composition.

Zhiwei Chan, Guolin Jing, Zhengnan Sun and Chen Zeng in 2018 introduced that chemical
modifications of waxy crude oil from traditional pour point to nanocomposite pour point
depressant resulted in the better results in the latter case since it restricts the formation of three
dimensional.

Crude oils containing large quantities of waxes, and in situations where sudden temperature
drops occur, a crystalline network can be formed, generating flow difficulties in production,
transfer and offloading lines. Despite the scientific and economic importance of this
phenomenon, correlations between the behavior of petroleum in relation to its pour point are
scarce in the literature. Many crude oil samples were characterized regarding density, water
content, wax fraction (one- and two-dimensional chromatography), pour point, yield stress and
wax appearance temperature.

The results showed that the storage conditions and oil characteristics had a strong influence on
the pour point. Yield stress was influenced by initial temperature of the sample, cooling rate and
shear rate during cooling. Finally, the content of aromatic compounds in oil with low
concentration of n-alkanes can contribute to increase the pour point was one of the result which
was concluded by doing the experiments.

The effects of the POA and POA/clay nanocomposite PPDs on the structural properties of
gelled Changing waxy crude oil were well studied through rheological tests, DSC analyses and
microscopic observation. Melt blending method was used here to prepare the poly (octadecyl
acrylate) (POA)/clay nanocomposite PPD, which shows much better performance on waxy crude
oil. The precipitated wax crystal amount of the crude oil at low temperatures does not change
with the addition of POA and nanocomposite PPDs, but the addition greatly weakens the
structure of the gelled crude oil.
CONCLUSION OF LITERATURE REVIEW

On individually increasing the PPD dose, the pour points of the model oil first decrease and then
increase, and nano-hybrid PPDs exhibit a better improved effect than pure EVA (VA = 32%).

 The nanoparticle with polymer coverage is another key determinant for the effect of
nano-hybrid PPDs, indicating that the compatibility between the stearic acid-modified
ATT and EVA is better than acetic acid-modified ATT

 Compared with 200 ppm dosage of Acetic acid-modified ATT(A-AtPPD(32)) and
modified nano-SiO2 composite PPD (N-SiPPD(32)), stearic acid-modified ATT (S-

AtPPD(32)) exhibits an improved effect, which decreases the pour point of the
model oil from 30°C to −1°C.

 Adding 400 ppm N-SiPPD (32) can decrease the pour point of the model oil from 30°C
to −3°C, but adding 200 ppm S-AtPPD (32) is more efficient and economic.

 It is worth noting that the viscosity of the model system composed of 200 ppm S-
AtPPD(32) is lower than that of 200 ppm N-SiPPD(32), and similar to that of 400 ppm
N-SiPPD(32). This also indicated that adding 200 ppm S-AtPPD (32) is more
efficient and economic.

 The decrease of the mean nanocomposite PPD particle size from 6 μm (prepared by
solvent blending) to 2 μm (prepared by melt blending) changes the dispersed state of
POA molecules in oil phase and thus greatly enhances the performance of nanocomposite
PPD.

 The WAT decreases from 30.3C to 27.3C after the addition of 200 mg/kg POA. After the
nanocomposite PPD is added, the WAT of the crude oil increases gradually from 28.2 C
at 200 mg/kg dosage to 29.0 at 400 mg/kg dosage, and then to 31.3 C at 800 mg/kg
dosage.
 CHAPTER - 3
MATERIALS AND METHODOLOGY

3.1 Materials used in the project :

 Crude oil
 Hexane
 Gas chromatography Apparatus
 Pour Point and Cloud Point Apparatus
 FTIR Apparatus
 Heating Mantle to heat crude oil to form liquid around 50-60 degree Celsius.
 Weighing Machine for density
 Nano-composite (carbon black)
 Polymers- PHPA
 Conitnuous Stirrer Apparatus
 Rheometer 301

3.2 Methodology :

First of all, Literature review will be carried out and information related to various problems
involved during the transportation of Indian heavy and waxy crude oils will be collected for different oil
fields of India. After then, heavy and waxy crude oil samples will be collected from the different Indian
oil fields. Fourier transform infrared spectroscopy (FTIR) (It is a technique used to obtain an
infrared spectrum of absorption or emission of a solid, liquid or gas. An FTIR spectrometer
simultaneously collects high-spectral-resolution data over a wide spectral range. This confers a
significant advantage over a dispersive spectrometer, which measures intensity over a narrow
range of wavelengths at a time.).

Rheological properties of oil samples will be investigated using a rheometer. Then Nano particle
based suitable surfactants (emulsifiers), pour point depressants (PPDs) and other requisite
additives will be identified and synthesized in the laboratory.
These synthesized nanocomposites /additives will be characterized on the basis of their physio-
chemical properties and by using analytical instruments like FT-IR and X-Ray Diffraction (XRD).
(It is a rapid analytical technique primarily used for phase identification of a crystalline material
and can provide information on unit cell dimensions. The analyzed material is finely ground,
homogenized, and average bulk composition is determined.)
Application of synthesized nanocomposites will be evaluated as surfactants and pour point
depressants to improve flow ability of Indian heavy and waxy crude oils, respectively, through
pipelines. Then pour point and rheological parameters of the prepared heavy crude oil emulsions
and treated waxy crude oils will be studied using pour point apparatus and rheometer,
respectively. Stability of prepared emulsions will also be investigated using bottle test method.
Further, the different factors such as Surfactant concentration, oil-water ratio, water salinity, pH
etc., which affect the flow behavior of emulsions as well as emulsion stability will be studied
thoroughly. For waxy crude oils, dosage of pour point depressants will also be optimized. A
particle size analyzer will be used to study the droplet size of oil in prepared oil-in-water
emulsions.
Experimental Procedure:-
For carrying out the required studies for the project, the laboratory is well equipped with state of
the art equipment, rheometer MCR301. The different parameters of oil have been measured with
standard(institute of petroleum) methods.
Procedure for determination of Density and API gravity of crude oil:-
Density of crude oil is measured by weight by volume method at 30 degree Celsius.
API Gravity is determined by the formulae:
0
API= 141.5/(S.G)-131.5
Procedure for determination of water content in crude oil:-
Water content is determined Dean Stark method. The procedure involves the taking of 50 ml of
crude mixed with same volume of toluene in flat bottom flask of the stark apparatus. The mixture
is heated to 85 degree Celsius and volume of the water collected in a graduated capillary tube
gives the water content of the crude oil.
Procedure for determination of pour point of crude oil:-
Crude oil is heated to 45-55 degree Celsius and cool inside the cooling bath. For every subsequent
decrease of 3 degrees Celsius, the pour point tube is removed and tilted to check the surface
movement when the specimen does not flow when tilted, the jar is held horizontally for 5 seconds.
If it does not flow, 3 degree Celsius is added to observed temperature and the result is pour point
temperature.
Procedure for determination of rheological properties of crude oil:-
The rheological properties of crude oil sample with and without chemical additives were studied
using anton par physica reheometer model MCR301 using cup and bob geometry with sensor
CC17 at shear rate of 1 to 60 s-1.
Setting conditions of Gas Chromatography

 First of all, set the Initial Temperature to 60deg. C for 2 minutes in the Method Editor.
Then, Set Ramp 1: 5.0 deg/min to 120 deg. hold for 5.00 min.
Ramp 2: 5.0 deg/min to 200 deg. hold for 5.00 min.
Ramp 3: 5.0 deg/min to 300 deg. hold for 5.00 min.
 Secondly, set the 65 min. Run-time for GC and MS.

Hexane A B Vial C D 
Figure 2. Samples Preparation for Gas chromatograph
 CHAPTER - 4

RESULT & DISCUSSION

The determination of physio-chemical parameter and reheological studies are the main tools for
characterization of crude oil for flow assurance. Flow assurance involves safe and efficient
delivery of hydrocarbon from the well to the collection facilities the various studies carried out
on the crude oil are described below in detail.

1. Weight of the Crude Oil was Calculated at 30 degree Celsius.

2. Density of water at 30 degree Celsius was found to be 0.995 gm/cc.
3. Density has been calculated by using weight by volume method and the resultant
density comes out to be 0.942:
Density = (Weight/volume)
Specific Gravity = Density of crude oil/ Density of water
(at same temperature)
S.G = 0.942/0.995 =0.9467
4. The API comes out to be 17.9612 which indicates that the crude oil belongs to the
black crude oil category and further studying out the properties of this crude oil
indicates that GOR is generally between 200-300 scf/STB and generally brown to
black in color.
5. Inititally, the cloud and pour point has been calculated using pour point and cloud
point apparatus and result come out to be
Cloud Point= 42 Celsius
Pour Point = 39 Celsius
6. Initially, the viscosity of the crude oil = 158 cp @21 shear rate
7. The Fourier transform infrared radiation and gas chromatography has been done
and the results are as shown
FTIR RESULT:

Figure 3. FTIR results depicting molecular composition and structure of Crude Oil Sample.
GAS CHROMATOGRAPHY RESULTS

Figure 4. Chromatograph for crude oil sample.

Table 1. Compounds present in Crude oil Sample

Initial Crude oil Results.

Data Series Information
Name: Crude oil without additive
Sample: Crude oil without additive

Shear Shear
Rate Stress Viscosity Yield Stress
[1/s] [Pa] [cP] [Pa]
7.38 2.35 319 1.3
8.18 2.42 296 1.3
8.97 2.49 278 1.3
9.77 2.55 261 1.3
10.6 2.62 248 1.3
11.4 2.68 236 1.3
12.2 2.74 225 1.3
13 2.8 216 1.3
13.8 2.85 207 1.3
14.6 2.91 200 1.3
15.4 2.96 193 1.3
16.1 3.01 187 1.3
16.9 3.07 181 1.3
17.7 3.12 176 1.3
18.5 3.17 171 1.3
19.3 3.22 166 1.3
20.1 3.27 162 1.3
20.9 3.31 158 1.3
21.7 3.36 155 1.3
22.5 3.41 151 1.3
23.3 3.45 148 1.3
24.1 3.5 145 1.3
24.9 3.54 142 1.3
25.7 3.59 140 1.3
26.5 3.63 137 1.3
27.3 3.68 135 1.3
28.1 3.72 132 1.3
28.9 3.76 130 1.3
29.7 3.8 128 1.3
30.5 3.84 126 1.3
31.3 3.88 124 1.3
32.1 3.93 122 1.3
32.9 3.97 121 1.3
33.7 4.01 119 1.3
34.5 4.05 117 1.3
35.3 4.08 116 1.3
36.1 4.12 114 1.3
36.9 4.16 113 1.3
37.7 4.2 111 1.3
38.5 4.24 110 1.3
39.3 4.28 109 1.3
40.1 4.31 108 1.3
40.9 4.35 106 1.3
41.7 4.39 105 1.3
42.5 4.42 104 1.3
43.3 4.46 103 1.3
44.1 4.5 102 1.3
44.9 4.53 101 1.3
45.6 4.57 100 1.3
46.4 4.6 99.1 1.3
47.2 4.64 98.2 1.3
48 4.67 97.3 1.3
48.8 4.71 96.4 1.3
49.6 4.74 95.5 1.3
 Observation table

S.No. Concentration Of Viscosity of crude oil Pour Point Of Crude oil. Shear Rate
-1
nanoparticle & polymer (cP) (deg. Celsius) s

0.05 gm 1ml 35 36 21
1.

0.05gm 2ml
34.3 36 21

2. 0.10gm 1ml 22.2 33 21

0.10gm 2ml 21.9 33 21

3.
Data Series Information
crude oil with 5 wt%additve
Name: 16.12.19
crude oil with
Sample: additve16.12.19

Meas. Shear Shear

Pts. Rate Stress Viscosity Yield Stress
[1/s] [Pa] [cP] [Pa]
1 7 0.356 48.2 0.0476
2 8.18 0.381 46.6 0.0476
3 8.97 0.406 45.2 0.0476
4 9.77 0.43 44 0.0476
5 10.6 0.453 42.9 0.0476
6 11.4 0.476 41.9 0.0476
7 12.2 0.499 41 0.0476
8 13 0.522 40.3 0.0476
9 13.8 0.544 39.5 0.0476
10 14.6 0.566 38.9 0.0476
11 15.4 0.587 38.3 0.0476
12 16.1 0.609 37.7 0.0476
13 16.9 0.63 37.2 0.0476
14 17.7 0.651 36.7 0.0476
15 18.5 0.671 36.2 0.0476
16 19.3 0.692 35.8 0.0476
17 20.1 0.712 35.3 0.0476
18 20.9 0.732 35 0.0476
19 21.7 0.752 34.6 0.0476
20 22.5 0.771 34.2 0.0476
21 23.3 0.791 33.9 0.0476
22 24.1 0.81 33.6 0.0476
23 24.9 0.829 33.3 0.0476
24 25.7 0.848 33 0.0476
25 26.5 0.867 32.7 0.0476
26 27.3 0.886 32.4 0.0476
27 28.1 0.905 32.2 0.0476
28 28.9 0.923 31.9 0.0476
29 29.7 0.942 31.7 0.0476
30 30.5 0.96 31.5 0.0476
31 31.3 0.978 31.3 0.0476
32 32.1 0.996 31 0.0476
33 32.9 1.01 30.8 0.0476
34 33.7 1.03 30.6 0.0476
35 34.5 1.05 30.4 0.0476
36 35.3 1.07 30.3 0.0476
37 36.1 1.09 30.1 0.0476
38 36.9 1.1 29.9 0.0476
39 37.7 1.12 29.7 0.0476
40 38.5 1.14 29.6 0.0476
41 39.3 1.15 29.4 0.0476
42 40.1 1.17 29.2 0.0476
43 40.9 1.19 29.1 0.0476
44 41.7 1.21 28.9 0.0476
45 42.5 1.22 28.8 0.0476
46 43.3 1.24 28.7 0.0476
47 44.1 1.26 28.5 0.0476
48 44.9 1.27 28.4 0.0476
49 45.6 1.29 28.3 0.0476
50 46.4 1.31 28.1 0.0476
51 47.2 1.32 28 0.0476
52 48 1.34 27.9 0.0476
53 48.8 1.36 27.8 0.0476
54 49.6 1.37 27.6 0.0476
Data Series Information
Name: crude oil with additive ( 0.10np)
Sample: crude oil with additive ( 0.10np)

Meas. Shear Shear

Pts. Rate Stress Viscosity Yield Stress
[1/s] [Pa] [cP] [Pa]
1 7 0.224 29 0.117
2 8.43 0.236 28 0.117
3 9.15 0.248 27.1 0.117
4 9.86 0.26 26.3 0.117
5 10.6 0.272 25.7 0.117
6 11.3 0.285 25.2 0.117
7 12 0.297 24.7 0.117
8 12.7 0.31 24.3 0.117
9 13.4 0.323 24 0.117
10 14.2 0.335 23.7 0.117
11 14.9 0.349 23.4 0.117
12 15.6 0.362 23.2 0.117
13 16.3 0.375 23 0.117
14 17 0.388 22.8 0.117
15 17.7 0.402 22.6 0.117
16 18.5 0.415 22.5 0.117
17 19.2 0.429 22.4 0.117
18 19.9 0.443 22.3 0.117
19 20.6 0.456 22.2 0.117
20 21.3 0.47 22.1 0.117
21 22 0.484 22 0.117
22 22.8 0.498 21.9 0.117
23 23.5 0.513 21.8 0.117
24 24.2 0.527 21.8 0.117
25 24.9 0.541 21.7 0.117
26 25.6 0.555 21.7 0.117
27 26.3 0.57 21.6 0.117
28 27.1 0.584 21.6 0.117
29 27.8 0.599 21.6 0.117
30 28.5 0.614 21.5 0.117
31 29.2 0.628 21.5 0.117
32 29.9 0.643 21.5 0.117
33 30.6 0.658 21.5 0.117
34 31.4 0.673 21.5 0.117
35 32.1 0.688 21.4 0.117
36 32.8 0.703 21.4 0.117
37 33.5 0.718 21.4 0.117
38 34.2 0.733 21.4 0.117
39 34.9 0.748 21.4 0.117
40 35.6 0.763 21.4 0.117
41 36.4 0.779 21.4 0.117
42 37.1 0.794 21.4 0.117
43 37.8 0.809 21.4 0.117
44 38.5 0.825 21.4 0.117
45 39.2 0.84 21.4 0.117
46 39.9 0.856 21.4 0.117
47 40.7 0.871 21.4 0.117
48 41.4 0.887 21.4 0.117
49 42.1 0.903 21.4 0.117
50 42.8 0.919 21.5 0.117
51 43.5 0.934 21.5 0.117
52 44.2 0.95 21.5 0.117
53 45 0.966 21.5 0.117
54 45.7 0.982 21.5 0.117
55 46.4 0.998 21.5 0.117
56 47.1 1.01 21.5 0.117
57 47.8 1.03 21.5 0.117
58 48.5 1.05 21.5 0.117
59 49.3 1.06 21.6 0.117
60 50 1.08 21.6 0.117
 CHAPTER - 5

CONCLUSION

 All the experiment results will show Physico-chemical characteristics like pour point,
cloud point, API etc. of Indian heavy/waxy crude oil samples like water content of
crude oil came to be 1% with high pour point .

 Gas chromatography (GC) was performed which is a common type of
chromatography used in analytical chemistry for separating and analyzing compo
vaporized without decomposition. Typical uses of GC include testing the purity of a
particular substance, or separating the different components of a mixture.

 FTIR analysis revealed the presence of various useful functions groups which
confirmed the existence of aromatics, phenols, alcohols, ethers, esters, and aldehyde.

 Rheological properties of the crude oil were calculated and viscosity was calculated at
different temperatures and shear rate using rheometer MCR-301.

 Carbon Black is found to be the most effective chemical additive for the crude oil in
reducing the viscosity and increasing the flowing properties of crude oil.
REFERENCES
[1] Wu, Y. M.; Ni, G. D.; Yang, F.; Li, C. X.; Dong, G. L. Modified Maleic Anhydride Co-
Polymers as Pour-Point Depressants and Their Effects on Waxy Crude Oil Rheology. Energy
Fuels 2012,26(2), 995–1001.
[2] Chen, S. K.; Oye, G.; Sjoblom, J. Rheological Properties of Model and Crude Oil
SystemsWhen Wax Precipitate Under Quiescent and Flowing Conditions. J. Dispersion Sci.
Technol.2007, 28(7),1020–1029.
[3] Yao, Bo & Li, Chuanxian & Yang, Fei & Sjöblom, Johan & Zhang, Ying & Norrman,
Jens& Paso, Kristofer & Xiao, Zuoqu. (2015). Organically modified Nano-clay facilitates
pourpoint depressing activity of polyoctadecyacrylate Fuel. 166.10.1016/j.fuel.2015.10.114.
[4] Ziyi Tu, Guolin Jing, Zhengnan Sun, Zhiwei Zhen & Wei Li (2018) Effect of
nanocomposite of attapulgite/EVA on flow behavior and wax crystallization of model oil,
Journal of Dispersion Science and Technology, 39:9,1280-1284,DOI:
10.1080/019322691.2017.1394187
[5] Edwards, R. T. Crystal Habit of Paraffin Wax. Ind. Eng. Chem. 1957, 49 (4), 750−757.
[6] Yao, Bo & Li, Chuanxian & Yang, Fei & Zhang, Ying & Xiao, Zuoqu & Sun, Guangyu.
(2016). Structural properties of gelled Changqing waxy crude oil benefitted with
nanocomposite pour point depressant. Fuel. 184. 544-554. 10.1016/j.fuel.2016.07.056.
[7] He, Cunzhe & Ding, Yanfen & Chen, Juan & Wang, Feng & Gao, Chong & Zhang,
Shimin& Yang, Mingshu. (2015). Influence of the Nano-hybrid pour point depressant on
flow properties of waxy crude oil. Fuel. 167. 10.1016/j.fuel.2015.11.031.
[8] Visintin RFG, Lapasin R, Vignati E, Antona PD, Lockhart TP. Rheological behaviour and
structural interpretation of waxy crude oil gels. Langmuir 2005;21:6240–9.
[9] Yang F, Zhao Y, Sjöblom J, Li C, Paso KG. Polymeric wax inhibitors and pour point
depressants for waxy crude oils: a critical review. J Dispers Sci Technol 2015;36:213–25.
[10] Norrman, Jens & Solberg, Amalie & Sjoblom, Johan & Gunnar Paso, Kristofer. (2016).
Nanoparticles for Waxy Crudes: Effect of Polymer Coverage and the Effect on Wax
Crystallization. Energy & Fuels. 30. 10.1021/acs.energyfuels.6b00286.
[11] Xu, J.; Jiang, H.; Li, T.; Wei, X.; Wang, T.; Huang, J.; Xu, Y. Effect of Comb-Type
Copolymers with Various Pendants on Flow Ability of Heavy Crude Oil. Ind. Eng. Chem.
Res.2015, 54(19),5204–5212.
[12] Machado, A. L.; Lucas, E. F.; Gonzalez, G. Poly (ethylene-co-vinylacetate)(EVA) as
Wax Inhibitor of a Brazilian Crude Oil: Oil Viscosity, Pour Point and Phase Behaviour of
Organic Solutions. J. Pet. Sci. Eng. 2001, 32(2), 159–1
[13] Zhang, J.; Wu, C.; Li, W.; Wang, Y.; Cao, H. DFT and MM Calculation: The
PerformanceMechanism of Pour Point Depressants Study. Fuel 2004, 83(3), 315–326.
[14] Ziyi Tu, Guolin Jing, Zhengnan Sun, Zhiwei Zhen & Wei Li (2018) Effect of
nanocomposite of attapulgite/EVA on flow behavior and wax crystallization of model oil,
Journal of Dispersion Science and Technology, 39:9,1280-1284,
DOI: 10.1080/01932691.2017.1394197
[15] Duffy DM, Rodger PM. Wax inhibition with poly(octadecyl acrylate).Phys
Chem:32834. 2002;4
[16] Duffy DM, Rodger PM. Modelling the activity of wax inhibitors: a case study
of Poly(octadecyl acrylate). J Phys Chem B 2002;106:11210–7.
[17] Peng, Z., Wang, W., Huang, H., Yang, S., & Gong, J. (2019, July 15). Influence of
Specific Surface Area and Morphology of Nanocomposite Pour Point Depressant on the
Modification of Waxy Oil. International Society of Offshore and Polar Engineers.
[18] Soni, H. P.(2008)."Performance-based designing of wax crystal growth inhibitors,”

[19] Zhiwei Zhen, Guolin Jing, Zhengnan Sun & Chen Zheng (2018) Nanocomposite pour
point depressants in improving the rheology of waxy crude oil, Petroleum Science and
Technology, 36:17, 1325-1331,doi: 10.1080/10916466.2018.1479421
[20] Song, X., H. Yin, Y. Feng, S. Zhang, and Y. Wang. 2016. Effect of SiO2 nanoparticles
on wax crystallization and flow behaviour of model crude oil. Industrial and Engineering
Chemistry Research 55(23):6563–8. doi:10.1021/acs.iecr.6b00836.
[21] Al-Sabagh, A. M., M. A. Betiha, D. I. Osman, A. I. Hashim, M. M. El-Sukkary, and T.
Mahmoud. 2016a. A new covalent strategy for functionalized montmorillonite-poly (methyl
methacrylate) for improving the flow ability of crude oil. RSC Advances 6(111):109460–72.
doi:10.1039/C6RA21319G.
[22] Yao, Bo & Li, Chuanxian & Yang, Fei & Zhang, Ying & Xiao, Zuoqu & Sun, Guangyu.
(2016). Structural properties of gelled Changqing waxy crude oil benefitted with
nanocomposite pour point depressant. Fuel. 184. 544-554. 10.1016/j.fuel.2016.07.056