Crude oil is the major source of energy today to meet our daily requirements. It is this crude oil that allows middle east countries to enjoy to an extent they want. However its life is diminishig slowly for more than 70% of it can’t be recovered under normal condition. No doubt secondary and tertiary recoveries are considered but their future is not encouraging with classical technologies, thus nanotechnological approaches are underway. The reason for this is that crude oil does not occur as pond under the surface of the earth. It migrates through sand bed, mostly in seconday rocks having specific porosity and permeability that changes from bed to bed across the journey of its migration. Crude oil does not migrate like river water. Sometimes it takes thousands of year to cover a migratory path because of its nature and several hurdles placed by nature – mostly a subject of petroleum geologists, helping exploration geologists to preoceed in for test drilling. Understanding this old science of crude oil migration and recovery in the light of nanotechnology is becoming a fashion in modern day research. Let us examine the fruitfulness of this subject in Indian context.

Summary: Tracing the migration path of Crude oil involves simple and complex materials from bulk organic compounds to traces of inorganic and biological residues along with active bacteria to virus to enzymes. The concentration of trace and rare materials depends on the genesis of formation and accumulation during the process of primary and secondary migration of crude oil. Those molecules that have played important role in the process of formation in the beginning are used later on as markers in biogeochemical exploration, an important modern day technique to explore crude oil in an efficient and cost effective manner. Among these molecules, biomarkers – molecules of bioinorganic and bioorganic origin, play key role in studying the genesis of crude oil and also help in tracing the migration path of crude oil when considered along with associated rocks, bacteria and formation water. The study is carried out in three phases. In the first phase the rheology of crude oil is studied and is co – related with the existing ones. The abnormal behavior is then studied with reference to water washing, bacterial degradation and porphyrin adsorption in the associated sedimentary rocks. It is established that the iron and magnesium from animals and plants based porphyrins are replaced by nickel and vanadium through participation of a virus during formation of crude oil. To what extent this original petro – porphyrin is degraded by available bacteria or washing from formation water or adsorption in the sedimentary rocks, is calculated and the respective trace metals nickel and vanadium are estimated. A given field is selected where maximum fractures and abnormalities are shown and a contour map is drawn from geological point of view taking petro – porphyrin based trace metals into account. Where from oil has migrated to this field and to which direction it has moved, is shown on the contour map and accordingly decision is taken by exploration geologists to proceed in for test drilling. It is to be noted here that nano – geology has already introduced to care finer points of crude oil migration.

How to initiate an Industrial Research program:This program is based on STEM culture. Reseachers from geology, chemistry, biolgy and physics along with technologists, environmentalist and managers can work together. Thus a team spirit and mutual respect for each other and proper interdisciplinary understanding is a must. It starts with understanding of the geology of that place where an oilfield is already developed. Oilfields may be a collection of shallow wells – below 1000 M or deep wells – deep as 4 to 5 KM. Most wells are vertically deep and some may be deviated from the vertical drilling route depending on the requirement or bindings because of the hard rocks. It is better to study the rheology of shallow wells and deep wells sparately. However after experience in this field one need not require such separation. A rough idea of grouping of the crude oil on the basis of API gravity is essential. this may be followed by the content of formation water. One should be very careful at this stage. If the water associated with crude oil is surface water or rain water, the study of that crude oil should be abandoned. Thus how to separate rain water or solvent water from formation water will be first training that can be had from text books. The separation of crude oil on the basis of composition is the next step. This includes hard crude and sweet crude. Hard crude and sweet crude must be separated to begin with. Generally only one type of crude oil is available in one oilfield – well exceptions are there. Collection of respective rocks from which the crude percolated out is the next exercise. Its composition and categorisation is important. While developing contour map this plays an important role for there is no exact mathematical fittings that controls the migration of crude oil under the surface of the earth though tried always. The entire findings are then synchronized on a simple surface map for discussion and debate. Please note there should not be any bossism in discussion – it must be thredbare in nature where even boss may not find a place to stand – thirty percent of the problems are solved on the surface of the brains if they are updated, clean, united and submissive in self.

Sample Collection: Sample collection is an art in such type of sensitive experiments. These samples can be collected from the surface through a common nozzle provided for this purpose and to release gas or to measure pressure associated with the incoming crude oil, flowing down to oil collecting stations for onward journey leading to separation of water and sands before allowing it to go for refining after subjecting to several treatments like API gravity or pour point depression check ups etc.
However while following the nanotechnological approach this classical approach should be replaced by direct collection of crude oil from the bottom of the well employing nickel samplers. These samplers are thin cylindrical pipes that are lowered inside the casing to collect oil in original form. After PVT treatment oil is released to normal condition. The first release is carefully examined for the presence of harmful bacteria. There are records that show these bacteria eating up the exposed skin of the field chemist while releasing oil. The presence of pathologist is a must during the first, second and third release. Once it is ascertained that such harmful bacteria are not present, the operation can be taken easily on daily routine. After collecting oils in high quality one liter plastic containers, these are allowed to stand at room temperature for seven to ten days. Glass vessels are never used for preserving such crude oil. The associated formation water is separated from each lot and examined following text book methods. The details of sample collection are recorded on a prescribed format, unique for each R & D Centers, and declared ready for experiment after preliminary physical examination and discussion with all concern. Each step is monitored brilliantely from the very first day. It is mandatory not to accept any oil sample for such an experiment on friendly basis. Each step undertaken should be open and transparent.

Crucial for India:
Lab and Industry links – The sample so prepared is divided in three parts. About 100 ml of the sample is preserved in the original container, 300 ml X 2 parts are distrubuted among two groups. One group may be from university or institutional laboratories while other group will be from the R & D Center of the same industry.
The university group may be asked to go into the basic research pertaining to its composition and related studies at major and minor level while the inhouse group may continue with the general findings that may lead to acquire a data leading to the preparation of contour map of oil migration. There is delicacy in both the works if taken seriously and outcome is always useful and interesting for two oilfields are never same in composition, behavior and prospects and there is always a chance for adding new findings going into the text books. There is scope for faculties from physics, chemistry, biology and mathematical modeling to work together in academic circles with their students while technocrats from various disciplines may join hands to find a solution pointer towards natural resource in demand employing their subject knowledge, skill, logic, integrity, zeal and field experience. However home work is a must!

Global Factors, Industrial Concern, Academic Interest and Future Economy: India is a country where people want more but do less. Most of their time is spent in blaming each other. Doctor blames engineere, barber blames blacksmith, cobbler blames goldsmith, manager blames farmers, teacher blames government and planner blames common man. The story is simple – Indian leaders are interested in such things. On the contrary the future of India is seen clean even by a lad running nacked on the streets for her future is rich – it is understood. Till recently even the lecturers of other discipline did not know GDP. And from that very juncture India had to move to compete with the developed nations. Also, front runners are yet to like competitors in their own stream but their days are numbered. On platform a scientist praises other scientist but when it comes to competition standing on the same platform the established one uses all his guns to kill his opponents. This applies in all fields.
Time has changed and each individual has to accomodate his challenger. Public – private partnership is not a choice but a compulsion from govt. side to meet requirements. Privately designed craze to harness everything overnight is another burden on care takers – there should be a balance between the two resources – human and natural to attain system’s stability. Thus systematization of systems in India has taken priority. Under this set of understanding there is a call of assimilation of knowledge for national development and personal advancement.
Global factors, industrial concern and academic interest can’t be separated for long when future economy of India is on stake. Even Americans have suffered for their last leg interest while trying to separate trio from the rest of their dealings and dwellings. Socio – scientific pact with environment has lasting impact on the total economy of a country when serious, sensitive and sharp intellectuals are on board. Future economy of India must not be seen separately from trio builders when planners and farmers are determined to meet the minimum requirements of individuals and daily wage workers – seemingly not a paper tiger!

Risk Factor and Sincere Initiation: The difference between an academic institution and a PSU lies on two simple considerations – People like to take risk on academic matters for it’s failure may not harm the general mass, however in a PSU this may have an upside down affect on major fronts. This is the reason why scientists and technologists employed in industry stay away from taking risk. In this case only risk can pave the way for better prospects. This risks are of two kinds – personal risk, associated with the undergoing experiments and the organisational risk that may compel system to pay huge sum of money as compensation to individuals. Both the risk factors are minimised on mutual understanding. The individual at work must be trained before undertaking such a project and the organisation has to remain loyal to the working group for the benefit mostly goes to the organisation in long run. In India this is the major problem – neither the individual wants to take risk nor the organisation is ready to encourage individual to go for taking such a risk by providing long term benefit. Time has changed; India is boosting to compete with the global market and thus the days of paper tigers like those of fullerene and superconductivity have gone and hence the new breed of managers, policy makers and scientists must share a common platform.

Estimation: Nickel and Venadium Petroporphyrins were used as biomarker in tracing the long range migration of crude oil since fifties but it’s authenticity was always questioned for several variables. Several changes have been incorporated now in the classical procedures to ensure reproducibility in the line of the requirements featuring efficiency. Of late nanotechnological inputs have been considered to refine the earlier analytical standings on calculation of nickel and vanadium content. The basic requirement in the present approach is to see that the adsorption of these elements are minimised on the glass surface of the container in which wet oxidation is carried out. This is done by allowing the constituents of the crude oil to get oxidised below 150 degree centigrade over a period of 13 hours. Thereafter a change in the procedure is applied to see that the porphyrin moity manages to form adduct with the fullerene content of the crude oil, either present from the beginning or generated during the process of slow oxidation in presence of fuming nitric acid, sulphuric acid and hydrogen peroxide added to 5 g of crude oil at an interval of 15 minutes. During this process the dangling bonds of fullerene are involved to form adducts with porphyrin by allowing nickel and vanadium cations to fall inside the cavity of fullerene. Once this happens the dark brown color of crude oil changes to yellowish brown. At this stage the wax of the crude oil is allowed to escape employing a temperature as high as 300 degree centrigrade. In classical methods the maximum temperature employed is 150 degree to avoid the escape of porphyrins that contain nickel and vanadium but in nanotechnological approach the metal content is captured inside the adduct cavity that takes care of the entity even at 300 degree centrigrade. Once the wax content and the excess sulphuric acid distill over the adduct gets ready to eject out metal content after rupture. A change in color from light brown to shining yellow results at this stage and several mild to strong explossions occur that signify complete separation of fullerene, free porphyrin and metal ions. The temperature is atomatically reduced for there is no more sulphuric acid. A clear transparent solution results at the end that is used for developing respective complexes for spectrophotometric estimation of metals in crude oil. This method is useful to calculate Ni and V to a lower level of 10 ppb. However the skill attached with the chemist on the bench matters.
What molecular nanotechnology is involved in this method: Capturing of metal ions in the porphyrin – fullerene cavity after rupturing the dangling bonds of fullerene allows to estimate concentration to ppb level. In classical methods one can estimate metal ion concentration only to a level of 2 ppm. It is not possible to go for wet oxidation of waxy crude at low temperature. However employing higher temperature means loss of petroporphyrins. Here metal ions are not allowed to get adsorbed on the surface of the glass while in cavity. Once the constitutents separate the nanoparticles of fullerene so released form a molecular layer on the glass surface of the container and thus metal ions remain unaltered in solution. The follow up details for drawing curve and estimation following Beer’s law can be had from any standard text book keeping in mind that the curve at lower concentration is never a straight line but a curve. The radius of curvature is important for one set of experiment. This changes with changing hands and glass equipments – however the difference should be less than 3 – 5 percent for skilled hands.

Caution: Wet oxidation of crude oil is carried out on less than 5 g of the original samples. There may be explossions during oxidation and severe cracking sounds during detachment of fullerene – porphyrin adduct containing NI – V ions in cavity – thus maximum care is important. Please don’t proceed without proper training and guidance for the behavior of each experiment is unpredictable.

Regards
Dr. R. Dayal Yadav
Director – Research
Study Group DIM.IUI