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Nanoparticles as an alternative to upgrade heavy oil by In Situ Combustion Process

Arturo J. Mendoza R.1, Mara A. Llamedo C.1, Susana Martinez1, Jess Amaro2,

PDVSA- INTEVEP1 - Petroleum Engineering School Universidad Central de Venezuela2 Caracas-Venezuela

This paper has been selected for presentation and/or publication in the proceedings for the 2013 Heavy Oil Latin America Conference & Exhibition [HOLA13]. The authors of this material have been cleared by all interested companies/employers/clients to authorize dmg:events (Canada) inc., the congress producer, to make this material available to the attendees of HOLA13 and other relevant industry personnel.

ABSTRACT Worldwide requirements of energy are increasing considerably as the main driving force to the development of the countries, but in the other side the limited resources of fossil fuel are contributing to look after new technologies to optimize the current processes in order to achieve these goals. The main sources of oil are concentrated in heavy oil unconventional reservoirs. Venezuela has been recognized as the owner of the biggest heavy and extra heavy oil reserves in the world. Therefore, an important opportunity and at the same time a crucial challenge to define the best scheme to exploit and produce from these reservoirs is being visualized. Conventional thermal recovery processes are not the best option to attain recovery factors higher than 10% in most of the cases. In the other hand, the oil produced is lean on its mobility properties and must be submitted to different processes on the surface to upgrade it previously to be refined and commercialized.

During the last ten years, different efforts have been carried out to optimize some of the thermal recovery processes in order to upgrade the oil from the reservoir which would be traduced in a higher commercial value. In Situ Combustion is considered a process feasible to be implemented in the Orinoco Oil Belt to improve production from this area, and its optimization using additives have been experimentally studied. Dispersed nanoparticles have been evaluated as an alternative to improve heavy oil properties using the energy generated by In Situ Combustion (ISC) process; promising results have been obtained: higher API oil gravity and lower viscosity, compared with conventional ISC; which implies higher value to the market. This could be a great opportunity to exploit and produce heavy oil reserves of Venezuela. Keywords: Nanoparticles, Heavy Oil, Combustion, Recovery Factor, Reserves.

INTRODUCTION One of the biggest challenges for the global oil industry is the extraction and production of heavy and extra heavy crude oil, mainly due to the most important aspect to consider, its low fluidity and/or high viscosity, which leads to the need to implement methods to improve its property. Thermal recovery processes are visualized as the best alternative with the potential to allow the production of the type of crude oil; however, the technological options should be easily applicable and economically feasible. It is well known the fact, that Venezuela has huge reserves of heavy and extra crude oil and bitumen nonetheless its efficient conversion towards commercial fuels continues as a technological challenge. In this sense, some technologies opportunities have emerged in the refining area, like deep conversion processes. Some of the emerging technology (CAPRI, THAI, etc.) at the reservoir that could be improved crude oil mobility in situ and minimizing costs of production and transportation. There are several theoretical proposals already described in patents and laboratory studies, based on different mechanisms of improvement crude oil properties as solvent injection, hydrogen donor, catalysts, biotechnology, chemical injection, microwave, in-situ combustion, etc. But among this group, highlights the In Situ Combustion, which has the additional advantage of being an implemented technology at the field worldwide (Venezuela, Romania, USA, Canada, India). It possible to mention some authors that support In Situ Combustion by its advantages: it is a thermal process for the recovery of crude oil wherein the heat transfer allows reducing the fluid viscosity and mobility contacted improving extraction and the recovery associated. (Cristofari, et al.,2008). Other author refer, In Situ Combustion has also demonstrated some additional benefits such as a very high thermal efficiency and low costs. (Turta, 1994) On the other hand, several countries like Romania, United Kingdom, Japan, United States, Canada, China, India, Argentina and Venezuela (Panait, A., 2006, Abuhesa, M., 2008, Kishita, A., 1998, Ramirez, M., 2008, Greaves, M., 2005, Wenlong, G., 2007, Doraiah, G., 2007, Cavallaro, A., 2008, and Mendoza, A., 2010) keep carrying out projects either to laboratory or field scale studies about the ISC process. The present experimental study has as main goal to evaluate In Situ Combustion Process using ultra-dispersed nanoparticles to optimize physical and chemical properties of heavy and extra heavy crude oil which could be potentially implement as a pilot test to the field in the Orinoco Oil Belt,

in order to improve the recovery factor and upgrading the crude oil .The scope of this study is to determine the guidelines and requirements to optimize the In Situ Combustion process with the incorporation of additives (nanoparticles), where the crude oil can get more value-added for the market. EXPERIMENTAL APPARATUS The physical displacement tests were performed in a system which included; crude, water and sand from the reservoir into a cylindrical steel cell; it was previously packed with sand trying to emulate reservoir conditions at laboratory scale (porous medium test). The cell configuration has different shots to record the corresponding temperature in this position of the cell and monitoring its variation in time once the test is started. All tests were performed in duplicate in order to validate the results in the cases studied. Fluids and sand used for the tests (oil, sand from the reservoir and formation water) were previously characterized in order to establish the changes produced once it is carried out the In Situ Combustion process without and additive (nanoparticles). To perform ISC tests requires thorough preparation. A detailed description of the process and equipment associated with the process is described following. COMBUSTION CELL Combustion cell comprises a cylindrical container constructed from 316 steel with dimensions 30.5 cm in length, 3.8 cm inside diameter, and 0.53 cm wall thickness. The cell withstands high pressures and temperatures (HPHT) and could operate to simulate reservoir conditions at laboratory scale. The test began by packing unconsolidated sand, oil, formation water and the fluid from a heavy oil reservoir, in order to determine the absolute permeability to the air and water. After that effective oil permeability was measured.

Figure 1: Steel Cell, Sand, Oil and Water in site Figure 2: Monitoring the Combustion Front Advanced Seven electric resistances are placed around the cell, each one with 150 cm in length. The first one is on top to promote the ignition, and the others keep the heat generated in the combustion cell during the test. The cell model facilitates the heat transfer. Also the air injection inside of it and the availability of sensors, spaced equidistant along its length, allow getting the temperature profile, and monitoring the combustion front in real time. The preparation of the cell is a fundamental part in the execution of a combustion test, which involves several procedures and determines the interval of time between consecutive tests. Generally, this period of time must not exceed one week (4 or 5 days should be sufficient), it began with preparation of the mixture of the hydrocarbon plus the additive or preparation of oil without additive; after it was packing, which made easy the permeability measurements for the fluids (gas, water, oil). Also pore volume, oil and water saturation are carried out before the thermal insulation. The cell isolation is critical, since excessive heat loss generated can promote the extinction of the combustion front. To maintain the combustion process, it is needed that the dissipated heat flux does not exceed the generated heat flow by the reaction. Under adiabatic conditions, it is possible to reduce this effect (loss heat). In order to have control and monitor continuously the system, the electrical resistances are placed throughout the cell body and then the cell is thermally insulated. After, it is heated on its surface to minimize or annul the temperature gradient generated by the combustion front inside the cell. Flow controllers allow the system control and regulation of the air injection rate. All generated data by monitoring is recorder every 30 seconds in a PC.

PROCEDURE AND EXPERIMENTAL METHODOLOGY There is no general consensus about the methodology and the system design for evaluate the ISC process although many groups have been working on it for more than two decades. It is still necessary know much about the system and the methodology used in order to establish criteria or improvements that could help future researcher studies in the ISC area. PDVSA Intevep developed a test system that offer important advantages like is fully automated facilities allowing the data collection, and easy manipulation of the cell due its small size; it measures only 30.5 cm, other additional advantage is the time it takes to perform a test. Other important considerations in the design of the equipment are related to the position and direction of air flow inside the cell injection. Mostly, these tests are performed with cell horizontally (Turta, A., 1994) which could promote gravitational segregation effect. Under this configuration, the air injected could not contact all the oil present in the medium, mainly the bottom part (from a crosssection viewpoint) is not affect by the ISC process. In these conditions the air injection could form fingering inside the cell, and just few amount of oil will be contacted and as a consequence the process efficiency would be lower. This recommendation motivated tests were performed on a vertical form where air is injected through the top promoting the heat front will spread downwards and thus ensure complete contact, the air flow is injected from the bottom

above, since by the effect of gravity as they displace crude front down and making contact with the hot sand and coke forming and covering sweep system. The tests conditions were established regarding to the area of study at the field (sand, pressure, temperature, permeability, from the reservoir, etc.); and it this sense would be possible to upscale the performance of the ISC process test to the field, providing an idea of the behavior of the important variables to be taken into account: amount of air required, consumed and recovered oil, etc. Five runs using crude 8.1 API from Orinoco Oil Belt were carried out, always keeping reservoir conditions. The first tests were reference; the following 4 trials were performed with additive and dispersed nanoparticles were evaluated as an alternative to improve heavy oil properties. All the experimental test were conducted under similar conditions, including air flow rate of 0.9 standard little per minute (slpm) and the reservoir defined equal to 1000 psia. The sand was packed in the cell, with a porosity of 30%, oil and water saturation of 83% and 17% respectively. The system was placed inside an oven and heated to reservoir temperature. After that, helium was injected to open a preferential path and thus avoid high differential pressure zone. Then, the ignition started when the temperature reaches 400 C. The air injected rate was 0.9 standard little per minute (slpm) (Grado, G., 2002) and helium injection in the cell was suspended. The beginning of combustion was indicated by the increase in the temperature sensors which were monitored in the console, the igniter was turned off when the combustion front passed through the first temperature sensor, the temperature generated was maintained adiabatically by the other resistances. When the combustion front passed for the last heat sensor the air was suspended. Before performing analysis it was determined the water content that accompanies each sample in order to verify the mass balance and to avoid any undesirable effect on the results. These results were used directly to evaluate the performance of the test and were also required for the calculation of recovery factor. The remaining oil contained in the sand was cleaned using a reflux column system in series with solvent (usually dichloromethane).

000 000
0

060

1
Air Air Helium

Figure 3: Schematic Experimental Apparatus

1 Flow Valve 4 Condenser 7 Pressure Transducer 2 Cell 5 Pressure Control Valve 3 Collector Cylinder 6 Flowmeter

RESULTS AND DISCUSSIONS All five (5) tests were conducted under similar conditions (pressure, temperature, etc.), the only variant that the test 1 was dry combustion conventional procedure, the test 2 and 3 were using an additive from effluent stream of refinery and the 4 and 5 the nanoemulsion. The following tables present the tests conditions, the characterizations of the fluids used and the mineralogical composition of the sand. Table 1: Combustion Run Conditions test CT
Sand Oil Volume (ml) Porosity (%) Permeability N2 (Darcy) Permeability H2O (Darcy) Permeability Oil (Darcy) Sw (%) So (%) Reservoir

1
Reservoir

2
Reservoir

3
Reservoir

4
Reservoir

111 32

111 29

123 33

131 36

122 33

4.4

3.6

3.6

4.8

3.9

4.7

2.1

6.2

4.1

3.5

3 8 92

1.5 20.7 79

1.4 13 87

1,8 20.9 79

2 16.6 83

It can be seen that slight variation on porosity this could be related with the differences in particle size and the amount of sand used instead permeability are very similar in each of the packed systems obtained. It is possible to observe in the Table 1 that the amounts and irreducible water saturations in trials from 2 through 4 remain remarkably stable, which is relatively normal since is the same sand which has similar characteristics; like wettability, which varies more with respect to the test Control Test (CT) in major proportion, it could be associated because oil sweep was more effective when it was saturating the system and it allowed a higher percentage of oil could displace water from the cell into the sand, however, this will not significantly affect or determine the final results. From the Table 2, it could be appreciated the main characteristics of oil, water and sand used in all tests. It is also important to mention, that the oil viscosity from a conventional ISC was 49,250 cP; but after incorporating additive either from effluent of refinery stream (tests 1 and 2) or the nanoemulsion (tests 3 and 4), the oil viscosity value reduces due to new interactions promoted between oil and added species, it brings as a results that the oil viscosity decrease with respect to the original oil. It is important to note that depending on the way how additives are added (either the effluent from distillation stream or nanoemulsion) in crude, this may generate effects on the performance of an ISC test. The studies carried out point it that the best alternative to disperse is in liquid form, and at reservoir temperature (323.15 K), seeking to obtain a dead crude mobility achieve a higher homogeneity of the mixture and thus ensure the success of the tests. Table 2. Test parameters, oil, sand and water properties.
API Gravity Water by distillation (Vol. %) Viscosity, cP @ 323.15 K Fe (mg/kg) Ni (mg/kg) V (mg/kg) SARA (% p/p) Water (mS/cm) Sand 8.8

Figure 4: Oil Recovery for Each Test

In Figure 4 oil recovery is represented by bars, the most important stage is the combustion; its produced the higher total recovery percentage, suggesting that this stage is the most representative of the physical simulation test for the oil displacement and improvement obtained. In another hand, it is possible observed that the recovery associated to each stage keep a trend line quite similar for all the cases considered in the comparison; and it showed that the recovery associated to combustion visualize an enormous opportunity as the technique to exploit and produce heavy and extra heavy oil. In the combustion stage, it is clear that oil production was equal for the entire test except for P1 test which showed a difference and it is motivated associated with its saturation in the medium. The crude consumed in all tests is similar, the presence of the additive catalytic nanoemulsion showed higher oil recovery (oil produced) compare with the tests P1, P2 and P3. In tests P1 and P2 in which there were increased oil consumption, it could be possibly associated to cracking reactions increased due to high temperatures and therefore coke deposition increased, thus the amount of oil consumed to increase. During evaluating the performance of each combustion test, can be noted that catalyst testing (P3 and P4) had a better performance than tests P1 and P2 without catalyst and therefore on average that can be attributed to a better oil sweep produced in a shorter time, which equates to lower costs and increase oil production. CT and P4 were the tests that higher oil recovery obtained (93.1 and 93% respectively), and although narrowly surpassed CT to P4, P4 was a test much faster than PC, finishing practically after 128.5 minutes and the CT test need 197 minutes to be completed. The

8.0

49250 5 92 400 10; 48; 27; 15 Distillated, 17660 98% SiO2; <1% Al2O3

requirement of about 60 minutes extra, it means to generate a lot of costs from the economic point of view to field conditions as CT needs more air and fuel compared to test P4, as well as highlight the other variables which possesses advantageous test P4; such as a considerable decrease of the viscosity and API gravity increased. Final results associated with the recovery show that the use of the nanoemulsion catalytic promotes higher oil recovery due to increased oil mobility and at the same time promote other mechanisms present in the process such as: evaporation, condensation, gas drive in solution, miscible displacement, vapor pressure, thermal cracking, etc., which may be related to an excellent high-temperature reaction of oxidation (HTO). MAXIMUM TEMPERATURE PEAKS Temperature is one of the most important parameters when it is evaluating an In Situ Combustion process, as such following it presents the flow and temperature profiles at standard conditions of the tests performed on the corresponding time after starting the ignition.

Table 3: Peak Temperature Variation for each ISC test

Thermocouple Tc-1 Tc-2 Maximum Temperatures (C) Tc-3 Tc-4 Tc-5 Tc-6 Tc-7

CT 400 572 350 572.75

P1 400.25 569.65 569.90 536.56 533.76 539.3 450.21

P2 385.16 616.72 688.75 599.92 556.52 512.47 401.28

P3 391.6 539.71 531.08 520,07 539.43 611.55 524.36

P4 426 548.67 512.91 495.44 506.93 558.98 483.02

517.36 482.36 400

Table 4: Time required for completing each test from ignition time until the end of the
Test CT 197 P1 155.5 P2 172 P3 120.5 P4 128.5

Temperature

Total time (min)

time

Thermocouple Position Front

Heat Wave

Figure 5. Temperature Profile versus Ignition Time

. . . . . .
Time (s)

Volum etric Flow (SLpm ).

Combustion Front Advanced

Figure 7. Combustion Front Advanced

Figure 6. Flow Profile versus Ignition Time In Figure 5 and 6, it is possible to observe a test characteristic behavior of the flow and temperature profile during ISC process; showing the temperature peaks corresponding to the front advance.

Figura 8. Thermocouple Across of the Combustion Cell

The average values of temperature shown in the Table 3 and timeouts lasting tests in the Table 4. A highlighted fact is that the duration of the tests; the control test (CT) takes longer than the test with additive; it shows an improvement in the speed which bring as a result; less time, lower air injected and faster production, all of these factors impacting on the economy. The first test was with catalyst nanoparticles ultradispersed P3 (Table 3), which was reported that more durable stability with very close temperature peaks for four continuous sections (or 4 thermocouples) from the thermocouple 2 to the 5, providing a higher performance compared with the other tests. Despite not achieving very high temperatures in the stabilized sections, it was very efficient sweep, allowing to achieve a high recovery (91.76%), and confirming that the use of catalytic nanoemulsion was not required to obtain a high temperature (530 C on average in the stabilized portions) and to have an excellent development cracking of the hydrocarbon molecules and positive results, which were located in the boundary of the high-temperature oxidation (HTO) zone, being the shorter test duration 120 minutes of running, generating better product than previous tests in lesser burning time. In this way, nanoparticles evidence is positive effect to improve ISC process, which using as catalyst ultradispersed showed in the results considerable variation in durability and stability of the temperatures reached, which could be look at optimal and ideal, compared with those obtained in the tests without catalyst ultradispersed (CT, P1 and P2). Table 5. Parameters Stabilized
Parameter Apparent Ratio H/C Ratio O2/Fuel (m3/Kg) Air Ratio/Full (m3/Kg) O2 Consumed (%) Excess Air (%) Fuel Requirement (Kg/m3) Air Requirement (m3CN/m3) CT P1 P2 P3 P4

In the Table 5, it shows the values of the parameters that were determined for each he tests of the ISC process, they were determined in stable periods. H / C with this parameter can determine the quality of crude oil burned, as temperature increases this ratio decreases by thermal cracking exists and consequently more coke and slowing the front. For the tests P3 and P4 tests increases this ratio while for the previous tests decrease. It could be associated with using the additive nanoemulsified promoted oxidation reactions at low temperatures, resulting from the thermal cracking as expressed (Tzanco, Moore, and Ursenbach Belgrave, 1991). Ratio Oxygen / Fuel (m /kg) while the process is more stable much oxygen reacts producing the typical products from combustion process. In all the tests was very similar behavior, noticing a slight increase in the last two tests (P3 y P4) as they required more oxygen for the stabilization since in the system was more fuel deposited in the medium to be burned. Air / Fuel Ratio (m /kg). is the amount of air required to burn a unit mass of fuel in the system. The results are very similar for all tests, it is important to mention that for the tests with additives although they were faster but the values obtained are similar, which is traduced that air requirement is lower. Oxygen (O2) Consumed (%). The oxygen consumed is mainly related with the fraction that react with the sulfur oxides; as shown in table 5 the fraction of oxygen to be convert in carbon oxides for the tests P3 and P4 was lower compared to the other tests. It results that not all fractions of the oxygen consumed would be came carbon oxides, and it would depend if there are no high-temperature oxidation, then the oxides react with carbon but also some portion of the oxygen reacts with the oil consumed forming oxygenates. This is manifested only on evidence as the tests P3 and P4 reached lower temperatures which could not allow high temperature oxidation. Fuel Requirement (kg/m ).The fuel requirement is usually expressed as the mass of fuel consumed per unit volume burned, and is a very important designs parameter for a ISC process (Prasad et al, 1986). This parameter is critical, because the combustion reaction generates residual fuel energy needed to sustain the combustion process (Bagci et al, 2001). The use of the nanoparticle ultradispersed is associated to an amount of fuel consumed per unit burned volume lower compared without additive tests (Table 5). This effect is positive, as it maintains the combustion front with a smaller amount of fuel, compared with the tests without catalyst,
3 3 3

1.2

1.3

1.2

1.6

1.8

2.2

2.2

2.3

2.4

2.4

1135 97.21 2.87

10.90 97.26 2.82

1103 94.72 5.57

11.59 95.21 5.03

11.66 95.67 4.52

45.34

64.05

123.86

35.67

32.10

515.35

699.07

1368.01

414.25

374.92

precisely because the swept volume of the stable area for catalytic tests is greater than the thermal generating; the fuel consumed is distributed in a homogenous way by volume scanning. The minimum difference of tests with nanoparticles 3 is up to 10 kg/m compared to the tests without catalyst (specifically, CT) giving a representative upgrade. P2 test evidenced that the amount of fuel requirement is 3 exaggerated (123.86 kg/m ) for the stable distance chosen, although revealing it unlikely that the process is applicable when there is little stability in combustion, despite reach high temperatures. Furthermore this evidence that more fuel would be associated to lower front speed of, this is confirmed as fuel deposition was higher for test without catalyst. Air Requirement (m CN/m ). Air requirement is the air 3 3 volume in m , required to burn the fuel deposited in one m of rock (Tadema, 1959). Through this parameter determines the performance of ISC process (Dietz and Weijdema, 1968). This variable has the greatest impact on economics ISC project, since it determines the compressibility of air (Rincon, 2002). In this study was observed that using catalyst the fuel requirement on the Table 5, both test P3 and P4 need a smaller amount of air to burn the fuel per unit volume in the area keeping a stable sweep. This effect is essentially to maintain the combustion front with a smaller quantity of air supplied, as compared with the tests without catalyst, precisely because the volumetric sweep of the stable area for catalytic tests is greater the thermals, generating the required air is distributed more homogenous in the porous medium to burn fuel per volume unit swept. The maximum saving referred to the air requirement to the 3 3 used of nanoemulsion on ISC process is up to 100 m S / m compared to the tests without nanoemulsion (specifically, CT). For the P2 test shows that the amount of air requirement 3 3 is exaggerated (1368.01 m CN/ m ) for the stable distance which was chosen, and reflecting it unlikely that the process is applicable where there is poor front stability ISC, in spite of reaches higher temperatures.
3 3

1.400

1.200

Concentration (% molar)

1.000

0.800

0.600

0.400

C6 C5 C4 C3 C2 C1

0.200

0.000

CT

P1

P2

P3

P4

Test

Figure 9: Light Compounds Produced during ISC tests The production of light oil compounds is an important parameter because it determines the amount of oil produced in a gas phase from the process. It could be considered as an indication of how productive and value added that would have the use of the catalyst in the process. In Figure 9, it shows the distribution of light compounds produced in the ISC process, which are encompassed by carbon number, starting from methane, and then having two carbon hydrocarbons, and so on until reaching compounds six carbons. It was also proved compounds as the amount of light increases when using the nanostructure catalyst in the process, showing that this additive promotes better reaction mechanism which positively influences the thermodynamics of the process during the burning of oil. This type of behaviour with a significant increase in light gases demonstrates the future potential of the use of additives ISC processes, giving an added value for the market.

SARA Analysis
60

50 P e r ce n t age (% p / p ) Original Oil Control Test 30 Test 1 Test 4 20

40

10

0 Saturated Aromatic Resins Asphaltenes

Figure 10: SARA Composition

Table 6. SARA Analysis

Percentage composition (%) Saturates Original Oil Test TC P1 Additive P2 P3 P4 15 9 7 11 16 10 Aromatics 48 Resins 27 Asphaltenes 15

Post Combustion 15 29 42 50 48 46 54 45 34 32 5.4 8 6 5 4

As for the content of asphaltenes in all tests can be seen a considerable decrease, Xia reported that asphaltenes are the main source for the formation of fuel in the process in order to maintain the combustion front (Xia et al, 2001). It means to have less asphaltenes evidence that the front fuel consumed formed. With respect to the saturated and CT tests, P3 and P4 were above the original crude oil giving added value to the oil produced in the tests; but P1 and P2 there is a loss may be because the light components were extracted as and therefore gas in the liquid is observed decrease. In general, with significant reductions in the asphaltenes fraction these results look very promising, and observed by the values obtained of test P3 and P4 being the best. Table 7. Viscosity of Crude

Sample

Viscosity (cP)

In the Table 6, it is possible to observe the SARA Composition of Original Oil with respect to the products obtained in the various tests. As shown in the Table 6 and Figure 10, the fractions recovered in the last stage of the combustion tests with and without additives, exhibit changes in the composition of SARA respect to the original oil sample. In three of the tests, a positive variations favor increase of the saturated compounds was determined, and one case shows an increase by 2% aromatics compound; for all the tests the resins increased and reduced asphaltenes fractions. SARA analyzed is a parameter to study in order to determine and quantify improvements in oil. Table 6 shows the composition of saturates, aromatics, resins and asphaltenes for CT test and P1, P2, P3 and P4 using additives. This table evidence that resins fraction has a predominant role specially for the test CT where increase by 19%, for the test P1 and P2 with effluent form distillation are an average of 49% with an increase of 22%, fort the tests P3, P4 have an average of 33% showing an increase over the original oil of 6% of all reported values, it could be related with the incomplete the thermal cracking that do not convert the overall resin molecules in asphaltene molecules (Eq. 1), due to the low process temperature. The aromatics for their part in testing CT, P1 and P2 show a slight decrease with respect to the original crude oil, while tests P3 and P4 are held on average, this because aromatics react with oxygen produce resins (Kok and Karacan, 2000) .
Hydrocarbon Aromatics Resin Asphaltene Coke

Original Oil Distillate and Oil Nanoemulsified and Oil Test CT P1 P2 P3 P4

49250 28740 40200 Viscosity (cP) 262.7 278.7 760.5 137.2 61.63

IMPROVEMENT OF CRUDE One of the most indicative improvements of the crude oil is reducing its viscosity, increasing H/C ratio resulting in low molecular weight hydrocarbons and in the reduction of the heavy fractions as asphaltenes. On the Table 7, it was observed an outstanding reduction of the oil viscosity in all tests, however for the tests P3 and P4 using the nanoparticle are far most remarkable since this leads to increased production of upgraded oil in the reservoir, this improvement could be associated with the high aromatic

Ec.1

content is a natural agent hydrogen donor. This study demonstrated that the use of nanoparticles in the ISC process allow to produce a crude oil with higher added value on the market.

simultaneously allows oil itself can be like a hydrogen donor when its has a high content of aromatics in the original structure (Wuitier, P.;1971, Rengel,P.; 2000) CONCLUSION

40 35 30

Additives in the form of nanoparticles ultradispersed contribute to stability of the front and increased speed without affecting the oxygen requirements. ISC using both additives evaluated in this study modify the physicochemical properties of the oil giving more value added in the market. Nanoparticles as additives ultradispersed are the best because they provide greater area of contact during ISC process. It was evidenced that the use of additives nanoemulsified promotes the formation/production of more upgraded crude. Upgraded crude oil produce by ISC with nanoemulsified additive imply several benefit associated to the process; increasing the H / C thereby increasing the low molecular weight hydrocarbons and thus increased mobility, asphaltene fraction is reduced. Hence the importance of proper selection of global process , and its implementation at the field with an additive which would be traduce in a pioneer technology with great potential for the exploitation of heavy and extra heavy crude at low cost.

A PI Gravity (A PI)

25 20 15 10 5 0

TC CT P2 P3 P4 Original Oil

Figure 11: API Gravity API GRAVITY ISC and cracking reactions using additive that occur during a displacement (physical simulation) test, generate substantial changes in the properties of the oil produced, as in API gravity. The calculation of this parameter is of vital importance, being the higher API gravity crude oil the lightest and also the most valuable in the world market.

ACKNOWLEDGMENT The work presented in this paper was supported by the National Oil Company of Venezuela (PDVSA) and the Research Institute (PDVSA-Intevep).The authors would like to thank to God Almighty and all work team involved in the development of this work, their technical discussion and especially to Maria Llamedo for her help to prepare the manuscript for publication.

Figure 12: API Gravity and Viscosity Relationship Figure 11 shows that the highest values API averages were determined for tests P3 and P4, in these tests are those using nanoparticle so its high performance could be attributed to the catalytic effect. It could also be attributed to the high content of aromatics fraction present in the original crude (48%), as the aromatic structures are stable at relatively low temperatures, but once them reached at 500 C, dehydrogenation reactions are presented; and

10

NOMENCLATURE = volume/volume, % = weight/weight, % = test number = hydrocarbon light compound (aliphatic and olefins) T1,T2,T3,T4,T5,T6 = peak temperature for each test, T1 (C), T2 (C), T3 (C), T4 (C), T5 (C) y T6 (C) S = saturation (%) H/C = hydrogen/carbon ratio Air/fuel = air/fuel ratio ISC = in situ combustion O2 = Oxygen Subscripts: o = oil w = water slpm = standard liter per minute v/v w/w CT, P1, P2, P3, P4 C1, C2,C3,C4,C5,C6

8.

9.

10.

REFERENCES 1. Abuhesa, M. and Hughes, R., Comparison of Conventional and Catalytic in Situ Combustion Processes for Oil Recovery, University of Salford, Manchester, U.K., November, 2008. Castanier, L., Baena, C., Holt, R., Brigham, W., and Tavares, C., In Situ Combustion With Metallic Additives, SPE 23708, Presented at the second Latin America Petroleum Engineering Conference, II LAPEC, of the Society of Petroleum Engineers held in Caracas, Venezuela, March, 1992. Castanier, L., kovscek, A., Heavy oil upgrading insitu via solvent injection and combustion: A new method, Conference & Exhibition, Madrid, Spain, 13 16 June, 2005. Cavallaro, A., Galliano, G., Moore, R., Metha, S., Ursenbach, M., Zalewski, E., and Pereira, P. In Situ Upgrading Of Llancanelo Heavy Oil Using In Situ Combustion and Downhole Catalyst Bed, University of Calgary, September, 2008. Cristofari, J., Castanier, L., and Kovscek, Laboratory Investigation of the Effect of Solvent Injection on InSitu Combustion, SPE 99752, June, 2008. Doraiah, A., Ray, S., and Guta, P., In-Situ Combustion Technique to Enhance Heavy-Oil Recovery at Mehsana, ONG- A Success Story, SPE 105248, Presented at the SPE Middle East Oil & Gas Show and Conference Held in Bahrain International Exhibition Center, Kingdom of Bahrain, 11-14 March ,2007. D`Silva, J., and Kakade, G., In-Situ Combustion with Solvent Injection SPE 117684, Presented at the

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2.

12.

13.

3.

14.

4.

15.

5.

6.

16.

7.

17.

2008 SPE International Thermal Operations and Heavy Oil Symposium Held in Calgary, Alberta, Canada, 20-23 October ,2008. Gonzlez, A., Diseo de Dos Equipos Experimentales (Tubular y Tridimensional) para Pruebas de Laboratorios In Situ a condiciones de Yacimientos, Tesis de Pregrado, Universidad Central de Venezuela, 2008. Grado, G., Estudio del Efecto de las Variaciones de Flujo y Concentraciones de Oxigeno del Aire Inyectado, en Pruebas de Combustin In Situ, Para Crudos Pesados, Trabajo Especial de Grado, Facultad de Ingeniera, Universidad Central De Venezuela, 2002. Greaves, M., Xia, T., and Ayasse, C., Underground Upgrading of Heavy Oil Using THAI (Toe- to Heel Air Injection), SPE 97728, Presented at the 2005 SPE International Thermal Operations and Heavy oil Symposium held in Calgary, Alberta, Canada, 1-3 November, 2005. He, B., Chen, Q.,Castanier, L., and Kovscek, A., Improved In-Situ Combustion Performance With Metallic Salt Additives, SPE 93901, Presented at the 2005 SPE Western regional Meeting held in Irvine, CA, USA, 30 March 1 April, 2005. Hernndez, N., Evaluacin Experimental del Proceso Combustin In Situ Empleando crudo de la Faja Petrolfera del Orinoco, Trabajo de Grado Presentado a la Facultad de Ingeniera, Universidad Central de Venezuela, 2003. Huseynzade, S., Upgrading and Enhanced Recovery of Jobo Heavy Oil Using Hydrogen Donor Under InSitu Combustion, thesis the Master of Science, Texas A&M University, December, 2007. Kishita, A., Tatsuo, K., Hong, C., Enomoto, H., Fundamental Study on a On-Site Upgrading of Sand, Journal of Japan Petroleum Technology, V.63, No.4, pp 337, 1998. Liguo, Z., Di, Y., Yuning, G., Ping, G., Lishu, Z., Changboa, L., Feasibility Study of the In-Situ Combustion in Shallow, Thin, and Multi- Layered Heavy Oil Reservoir, SPE 117638, Presented at the 2008 SPE International Thermal Operation and Heavy Oil Symposium Held in Calgary, Alberta, Canada, 20-23 October, 2008. Mendoza A., Perozo H., Oliveros D., Reyes N.; Study for Improving the In- Situ Combustion of Venezuela Extra-Heavy Crude, Oil Using Unconventional Additive; (SPE), LACPEC. Lima, Peru, December, 2010. Mendoza A.,Perozo H., Oliveros D., Reyes Nelson., Reinoza J.;Estudio preliminar para optimizar la tecnologa de Combustin En Sitio con uso de

11

18.

19.

20.

21.

22.

23.

24.

25.

26.

aditivos para crudos pesados de la Faja Petrolfera del Orinoco. Presentado en las Jornadas de Investigacin de la Facultad de Ingeniera (JIFI). Universidad Central de Venezuela, Noviembre, 2010. Mendoza, A., Perozo, H., Oliveros, D., Reinoza, J., Rivas, A., Arellano, D.; Estudio Experimental Novedoso Usando un Aditivo Emulsionado Para El Mejoramiento Del Crudo Pesado De La Faja Petrolfera del Orinoco con la Tcnica de Combustion En Sitio; INGEPET, EXPL-3-AM-10-E, Lima, Peru, 2011. Mendoza, A., Oliveros, D., Arellano, D., Perozo, H., Reinoza, J, Rivas, A.; New approach to upgrade the Combustion In Situ Process by using an Emulsified Additive on Heavy Oil from Orinoco Belt, Enhanced Oil Recovery Conference, Kuala Lumpur, Malaysia, 2011. Mendoza, A., Perozo, H., Oliveros, D., Reyes, N., Reinoza, J.; Study for Improving the In-Situ Combustion of Venezuela Extra-Heavy Crude Oil Using Unconventional Additive, World Heavy Oil Congress, Edmonton, Canada, 2011. Mendoza A., Perozo H., Arellano D., Oliveros D.; New Insights from the comparison of conventional, catalytic and emulsified additives in Situ Combustion Process to upgrade heavy oil recovery. AberdeenReino Unido, WHOC-2012 Nares, H., Schacht, P., Ramirez, M., and Cabreras, M., Upgrading Heavy and Extra Heavy Crude Oil with Ionic Liquid, SPE 108676, Presented at the international Oil Conference and Exhibition in Mexico held in Veracruz, Mexico, 27-30 June, 2007. Panait, A., Serban, D., and Ilie, N., Suplacu de Barcau Field A Case History of a Successful In-Situ Combustion Exploitation, SPE 100346, Presented at the SPE Europec/EAGE Annual Conference And Exhibition Held in Vienna, Austria, 12-15 June, 2006. Prasad, R.S., and Slater, J.A.; High Pressure Combustion Tube Tests. Paper SPE/DOE 14919. Tulsa, Oklahoma, USA, pp. 503 510, 1986. Ramirez, M., Hernandez, M., Cabrera, M., Schacht, P., Instituto Mexicano de Petrleo, and Mamora, D. Increase Oil Recovery of Heavy Oil in Combustion Tube Using a New Catalyst Based Nickel Ionic Solution, SPE 117713, Presented at the international Heavy Oil Symposium held Calgary, Alberta, Canada, 20-23 October, 2008. Ramirez, M., Mamora, D., Nares, H., Schacht, P., Mohammad, A., Cabrera, M., Increase Heavy Oil Production Tube Experiments Through the Use of Catalyst, SPE 107946, Presented at the 2007 SPE Latin America and Caribbean petroleum engineers

27.

28. 29.

30.

31.

32.

33.

34.

35.

36.

37. 38.

conference held in Buenos Aires, Argentina, April 2007. Rengel P., Puesta a Punto de un Reactor tipo Batch para experimentos de Mejoramiento de Crudo a condiciones de baja severidad, Informe de Pasantia, Departamento de Procesos Qumicos, USB, Sartaneja ,2000. Reza S.,Catalytic Process Petroleum Refining, 2003. Rincon, A. Recuperacin Trmica de Petrleo, Recopilacin y Manual. UCV, Caracas, Venezuela, 2002. Sarathi, P.S., Nine decades of combustion oil recovery-a review of in situ combustion history and assessment of geologic environments on project outcome, Proc. 7th UNITAR International Conference on Heavy Oil and Tar Sand, Beijing, China, 27-30 October, 1189-1200, 1998. Turta, A., Evaluation of IOR Potential of Petroleum Reservoirs. Institute de Recuperation the Petroleum, Alberta, Canada, 1994. Vallejos, C., Hernndez, N., Lamus, J., Vzquez, T., Tendencias Globales en el uso de la Tecnologa de Combustin In Situ para el Mejoramiento en el Subsuelo de los Crudos P/XP, Informe Tcnico INT7690, Los Teques, Venezuela, Octubre, 2000. Vzquez, D., Izarra, N., Albornoz, O., Oliveros, D., Mendoza, A., Sastoque, M., Hernndez, N.,Estudio experimental del proceso de Combustin en Sitio para el campo Bare Arena R0, Utilizando Arena de Formacin con Tamao de Grano Mayor a 75 Micrones, Informe Tcnico, INT 12716, Los Teques, Venezuela, Marzo, 2009. Weissman, j., Review of Processes For Downhole Catalytic Upgrading of Heavy Crude Oil, Fuel Processing Technology, USA, 1997. Wenlong, G., Shuhong, W., Shihu, W., Junhe, C., and Yaping, C., Physical Simulation of In-Situ combustion of Sensitive Heavy Oil Reservoir, SPE 110374, Presented at the 2007 SPE Asia Pacific Oil & Gas Conference and Exhibition held in Jakarta, Indonesia, 30 October 1 November, 2007. Wichert, G., Okazawa, N., Moore, R., and Belgrave, J., In-Situ Upgrading Of Heavy Oil by LowTemperature Oxidation in the Presence Of Caustic Additives, SPE 30299, Presented at the international Heavy Oil Symposium held Calgary, Alberta, Canada, 19-21 June, 1995. Wuitier P., El Petrleo: Refino y Tratamiento Qumico, ediciones CEPSA, Madrid,1971. Xia, T.X., and Greaves, M. In Situ Upgrading of Athabasca Tar Sand Bitumen Using Thai; Tras IChemE, Part A, Chemical Engineering Research and

12

Design, 84(A9): 856-864, 2006.

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