1

Study about oil sands and bitumen

extraction methods

Figure 1.1. Munaily Mola oil sands.

Escola Tcnica Superior de Enxeara (ETSE)

Universidade de Santiago de Compostela( USC)

Institute of Combustion Problems

Al-Farabi Kazakh National University

Sal Domnguez Negreira, 3 Grao en Enxeara Qumica (USC)

Supervisor: Profesor Mansurov Z.A. and PHD Tileuberdi Yerbol

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Index

1. Introduction..........................................................................3

2. Materials and experimental methods.....................................12

2.1. Extraction with chloroform..........................................12 2.2. Thermo-contact method..............................................14 2.3. Fractional analysis........................................................15 2.4. Clay extraction.............................................................16 2.5. Elemental analysis........................................................17 2.6. Microscopic analysis....................................................17

3. Results and discussion.............................................................18

3.1. Extraction with chloroform..........................................18 3.2. Thermo-contact method..............................................20 3.3. Fractional analysis........................................................26 3.4. Clay extraction.............................................................28 3.5. Elemental analysis........................................................28 3.6. Microscopic analysis....................................................30

4. Conclusions..............................................................................33

5. Bibliography.............................................................................34

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1. Introduction

Oil sands, also called "tar sands " or " bituminous sands", are a mixture of sand, water and bitumen, the proportions of these different components vary depending on the country where this valuable mixture is analyzed and the deposit where it is found. Nevertheless, the percentage of bitumen into this ore is always between 1% and 20%.[1] Bitumen is a very low grade crude, extremely viscous at the temperature of the reservoir and has a very high sulphur content ( about 5% ). Other undesirable qualities in the bitumen are those of having troublesome amounts of nitrogen and oxygen as well as high contents of heavy metals. For these reasons, it is not possible to use bitumen directly as a feedstock for conventional petroleum refineries, it has to be processed first to upgrade it so that can be useful as raw material. Besides, bitumen can be solid in a cold environment and, because of this, the traditional extraction methods do not work.[1,2] However due to the uncertainty about foreign oil supply those countries with high external oil dependence are performing an industrial use of these oil sands to produce their own oil. Besides, because of the increasing of the conventional petroleum prizes, some oil producing countries start to use their oil sands reservoirs to increase their production. Although the costs of obtaining fuels from oils sands are quite higher than those of the conventional oil, the shortage of this fossil fuel and the rise in its price are leading to a more extended use of unconventional oil sources. [2] When it comes to explain the origin from the different oil sands from the world there are two main theories. The first one suggests that the oil sands come from the degradation of conventional petroleum during long periods of time by microbes that left behind some bitumen and converted the lighter crude into heavier fractions. The second one does not assume that the petroleum formation cycle was completed and explains the origin of bitumen as the incomplete or anomalous process of formation of oil from organic matter.[1]

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The next figure shows the process of bitumen formation including the two possibilities: Figure1.2: Diagram of the petroleum formation process

Through Diagenesis , the organic matter is compacted under mild conditions of temperature and pressure. In marine environments, the deposited organic sediments are saturated with water. Through chemical reactions, compactions and microbiological activity the water is expelled out of the sediments and the organic molecules are broken down to form new structures to form kerogen ( waxy material) and bitumen.[1] Catagenesis occurs when the burial deep is increased with the time. Higher temperatures and pressures start the process by which the kerogen transformed into hydrocarbon chains by a cracking process. The length of these hydrocarbon chains depends on the extent of the degradation of the kerogen ( depending on the temperature and pressure).[1] According to the first theory, the petroleum formation process was completed and then it was transformed in bitumen due to the activity of the microbes. But according to the second theory, Catagenesis did not occur because the organic matter was not buried deep enough and the kerogen was not transformed into hydrocarbons. It was just under very long periods of time that some portion of the kerogen was transformed into bitumen.[1]

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Although oil sands can be found in many countries around the world, the vast majority of their reserves are in Canada and Venezuela in a lesser extent. With approximately 2.1 million barrels of oil trapped under the state of Alberta, Canada possesses the largest single reserve of oil in the world. However, other countries such as Kazakhstan or Russia have considerable amounts of this ore too. In fact, the focus of this study are Kazakhstan oil sands and , this country, has over 50 fields of oil-bituminous sands being some of the most important deposits those of Beke and Munaily Mola regions. For now, it is not needed or profitable for the Kazakh to start obtaining petroleum form oil sands as long as they large oil reserves are still far from depletion. However, it is interesting for them to find a way to obtain this "Black Gold" when their country run out of conventional oil sources. [1,3,4] Although this study is going to be focused in Kazakh oil sands, a continuous comparison with Canada will be made due to its high relevance in the oil sands world (at least in this section). In the next figures, it is shown where the biggest areas of oil sands are found in Kazakhstan and Canada.

Figure 1.3 Canada oil sands deposits. Figure 1.4. West Kazakhstan oil sands deposists.

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As it was said before, traditional extraction methods are not suitable for bitumen recovery so , when the Canadians started to extract oil sands from their deposits, they had to remove the layer of ground that is over the wanted ore (including trees and all kind of life that could exist in that level) so that the oil sands could be extracted as a surface mine. However, more modern extraction methods have been developed to overcome this problem such as "in situ" extraction methods that are more environmentally friendly and avoid the need to remove the upper layer of the ground.[2] The surface mining extraction method is similar to many coal mining operations. In Alberta, the top overburden layer is a mass of decayed vegetation called muskeg, going from two to twelve feet deep that must be drained with systematic ditch arrangements after all existing streams in the area have been diverted and takes between 2 or 3 years. After that, the trees of the area can be cut and the top layer of ground can be removed with heavy mobile equipment such as bulldozers and trucks. In this region winter is the season chosen for doing this process because the muskeg is frozen and the movement of the heavy mobile equipment is improved. Besides, the muskeg is stored for recovering the area after the mining in that place is finished and the rest of the top ground layer is used for making ponds for the extraction plant ( will be explained later). [2,5] After the process of the overburden layer removal, large shovels scoop the oil sand into trucks that then take it to crushers where the large clumps of earth are broken down. For improving the transport of this material to the plant the oil sands are thinned out with water and , once in the plant, the extraction of bitumen is performed. Kazakhstan has not started yet to mine its oil sands so it is not possible to compare its methods with the Canadian ones . The next figure shows a typical surface mining scenario . [2,5] Figure 1.5 Surface mining scenario with heavy mobile equipment with the overburden layer already removed.

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Despite the fact that the most employed method for taking the oil sands from the ground in Canada is the surface mining almost the 80% of the Alberta oil sands are out of the reach of surface mining. In situ methods are used to recover bitumen that is found too deep for the other method to be useful. These kind of methods are based on reducing the bitumen viscosity thanks to a temperature increase so that it will flow and be taken from deep in the earth. Despite implying a higher amount of energy and water than the surface mining method the in situ methods are less harmful with the nature and are the only way take the bitumen from such deeps. Besides, these kind of methods are expected to be more profitable in the future as research keeps developing. Steam Assisted Gravity Drainage (SAGD) and Cyclic Steam Stimulation (CSS) are the two major methods used nowadays as in situ extraction methods. [6] The CSS method uses steam at high pressure and temperature to inject into a wellbore made into the oil sands, the high pressure steam fractures the oil sands and starts to soak them. Since the steam is at a very high temperature it melts the bitumen and makes it flow to a producing well, from which it is pumped to the surface.[6] The SAGD method uses two horizontal wells through the deposit. From the upper well high pressure steam is injected into the sands melting the bitumen and forcing it to flow to the second well from which is pumped to the surface. At the same time, water is injected too to keep the stability after the removal of the bitumen.[6] In the next figure it is shown the Schematic of a SAGD in situ development:

Figure 1.6. Schematic of a SAGD in situ development

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With in situ extraction methods there is no need to extract the bitumen from the sands because it is already separated when it is collected. However, with the surface mining procedures bitumen must be separated from the rest of the mixture that comes with it. In Canada, the most extended process for the separation is the "hot water process".[2] The hot water process starts with a conditioning step where the raw oil sands are mixed with hot water and their temperature is risen up until 85C. Then, the PH of the mixture is changed to 8-8.5 with the addition of a NaOH solution( for improving the separation). Besides, the mixture is agitated in rotary drums and steam is continuously added to keep a constant temperature. Under these conditions, the bitumen stuck to the sand is released from them producing a mixture of particles of sand and globules of bitumen in a matrix of water. [2] After that, the mixture is screened to separate too big particles and then poured into a settling tank where the mineral particles settle down. At the same time, the bitumen globules rise up to the surface forming a frothy layer which is sent to the next process stage while the sand of the bottom is sent to a tailings pond. The mixture in the middle of the upper layer( bitumen) and the bottom layer( sands and water, tailings) is recirculated to the settling tank to increase the yield of the process and another part of it leaves to further separation. In this second separation unit the bitumen is separated with the injection of air and agitation, this leads to the formation of another frothy layer that is sent to another settler to improve its quality( the tailings are sent to the pond) and then mixed with the bitumen stream obtained from the first unit separation ( the tailings of this unit is sent again to the separation unit of injection of air and agitation). [2] The bitumen stream ( formed by the two previous frothy streams) is mixed with naphtha ( 50/50 mixture) to reduce its density and enhance the separation of water and entrained solids in a two stage centrifugal process. The tailings from each centrifugal step are mixed and sent to the tailings pond and the product obtained is a mixture of naphtha and bitumen with 0.5% of solids and 4-7% of water ( weight/weight).[2] In the next figure a simplified Process Flow Diagram of the hot water process is shown to facilitate the comprehension of the process explained before.

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Figure 1.7. Suncor system flow-chart hot water process.

Despite that Canadian industries have been using this method for decades, the environmental problems related with it are quite important. The two main drawbacks of this process are the big amounts of water required for making one barrel of oil and the big amount of tailings produced. Besides, the energy consumption is also very important. For producing one barrel of oil the industries that use this process require from 17 to 21 barrels of water, however, the majority of this water is recycled and just from 2 to 4.5 barrels are needed( which is a lot anyway). Also, large tailings ponds are required to contain the unsettling and unconsolidated tailings, which have accumulated to about 650 million m3 by 2006.[7] Kazakh scientists, nowadays, are developing mainly two methods for taking the bitumen out of the oil sands. Although there is not any developed industry for this extraction methods their studies are giving quite good results and their non aqueous process are likely to be used in a real Kazakh oil sands industry. The first of these methods is called the thermo-contact method, this process consists on a reactor where heat is applied to the system (the oil sands are inside it ) achieving a temperature between 450 and 550 C and a condenser that leads to a storage vessel .

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The high temperatures volatilize the organic compounds of the oil sands so that they leave the reactor and are condensed in the heat exchanger and poured into a storage vessel. Thermal breakdown of the big molecules is also produced. Besides, because of the high temperatures, the sands and the clay act as catalysts in the breakdown of the large molecules of the bitumen to form shorter chain molecules and some coke. Depending of the temperature different products can be obtained and almost all the organic matter leaves the reactor except some coke that can be retained stuck to the walls of the reactor. With a good controller the temperature can remain constant very easily. In the laboratories, this process has just been tested as batch ( an insulated reactor and a tube that leads to a simple condenser made of glass). Low heat losses and well closed pipes are essential to a good process performance as well as an effective condenser. The second method used by Kazakh scientists is the extraction with chloroform as a solvent. It is performed in the lab with a Soxhlet apparatus that can be simplified as a multi-stage contact extraction with using always pure solvent. The scheme of the process would be shown in the next figure.

Figure 1.8 multiple stage contact extraction where D means solvent, R means refine and E means extract. The sub index refer to each stage of extraction.

In Figure 1.8 , all the extracts (E) will mix together and the solvent would be separated from the solute by evaporation.

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Now the real Soxhlet apparatus is shown to compare with the previous scheme.

Figure 1.9. Soxhlet apparatus scheme. Scheme of the system used for the extraction. 1: Stirrer bar 2: Still pot (the still pot should not be overfilled and the volume of solvent in the still pot should be 3 to 4 times the volume of the Soxhlet chamber) 3: Distillation path 4: Thimble 5: Solid 6: Siphon top 7: Siphon exit 8: Expansion adapter 9: Condenser 10: Cooling water in 11: Cooling water out

Chloroform has been proved to be a very good solvent for the hydrocarbon mixture of the oil sands. However, the solvent losses can be a problem in a big scale oil sands plant although it is more efficient if the extraction set up is carried as a countercurrent process and carried out as continuous. In this study, these methods will be analyzed experimentally treating Kazakh oil sands.

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As it was mentioned before, bitumen cannot be used as feedstock for refineries due to its chemical and physical properties. For that reason, it must be upgraded to obtain a product than can be used as normal petroleum. There are several upgrading methods, the Coking process uses heat to break the long chain molecules into smaller molecules and producing coke at the same time that can be used as fuel for the process. The thermo-contact method described before does the same but in a much smaller extent and it mainly vaporizes the organic compounds. Catalytic Conversion has the same aim of the Coking process but it uses a catalyst to enhance the breakdown of the compounds, sometimes hydrogen is added to stabilize unsaturated compounds. Distillation is another method whose aim is isolate certain compounds of the bitumen along a rectification tower(s) , kerosene naphtha and light gas oil are the main fractions collected. Finally the Hydrotreating process mixes the heated bitumen with hydrogen at high pressure and temperature to saturate the unsaturated molecules and reduces impurities such as sulfur, nitrogen or trace metals.[8]

2. Materials and experimental methods.

In this section, different experiments relating oil sands were performed to get a better understanding of this natural ore. 2.1. Extraction with chloroform. For this experiment only Munaily Mola oil sands were used because the aim of that experiment was just to understand better the content of bitumen of the oil sands. First, oil sands from Munaily Mola deposit were ground manually to improve the contact surface for the extraction. After that, the sands were covered with filter paper( already weighted) and insured with a cordon of negligible weight . The wrapped sands were weighted and then put into a system formed by a Soxhlet apparatus, a reflux condenser, a flask, a heating plate and an upright so that the extraction could be performed properly.

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The system is represented by the following figure:

Figure 2.1. Soxhlet apparatus scheme. Laboratory installation extraction to extract the organic part of petroleum bitumen rock1 Return water cooler, 2 extraction nozzle, 3 flask, 4 electric range, 5 Holder

Using chloroform as solvent, the extraction began by introducing it from the top of the system and then, returned from the flask to the top due to the boiling of the chloroform from the solution obtained. The process was left working for a couple of days. The efficiency of extraction is assumed to be 100%. After the extraction, the mixture of chloroform and bitumen ( that remained in the flask of the bottom of the system previously described ) had to be distilled to separate both components, with a simple lab heat exchanger and the appropriate connections as well as a flask to recover the distillate, both components were separated. The chloroform that remains in the oil sands after the process ( inert) volatilizes very quick so that it all disappeared before the weighting. At the same time, the wrapped oil sands were separated from the filter paper and then poured into some Petri dishes already weighted to directly obtain a measure of the mass of the sands. The filter paper was also weighted to know the amount of sands that it might had absorbed during the extraction.. The sands obtained after the extraction were dried in an oven to know how much water they contained.

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The next two figures show the extract obtained( with some chloroform still in it) and the oil sands after the extraction and the drying.

Figure 2.2 Extracted bitumen and dried oil sands

2.2. Thermo-contact method. Oil sands were put (measured amount) into a reactor and heated through an electrical resistance , the temperature inside the reactor was maintained thanks to a simple controller that turns on and off the current to the resistance when the T inside the basin exceeds or falls from the set point respectively. The reactor is a cylindrical basin with a length of 20 cm and an inner diameter of 8 cm. [9] Due to the high temperature achieved inside the reactor, all the organic fractions of the bitumen boiled and just the inorganic sands remained in the basin. The thermal breakdown of the big molecules into smaller ones is also produced. The exhaust tube of the reactor leads to a heat exchanger where the vapors are condensed and poured into an Erlenmeyer flask. It must be said that ,in a little extent, the thermo-contact method is also catalytic, the clay and the heavy metals present in the mineral phase of the oil sands act as catalyst so that heavy fractions of the bitumen react to form lighter parts.

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Two different types of oil sands were tested in this experiment. First, Munaily Mola sands were processed with the thermo-contact method repeating the experiment for different temperatures and times inside the reactor and then the process was repeated with Beke oil sands. Two different temperatures were used, 450C and 550C, and for each one two different times, 45 minutes and 60 minutes. In the next figure, a photo of the reactor operating is shown.

Figure 2.3 Operating reactor with the heat exchanger , the storage flask and the temperature controller

2.3. Fractional analysis. Bitumen obtained with a extraction method, bitumen obtained through thermo-contact method and oil sands after the extraction and after the thermo-contact method were analyzed. The bitumen was distilled heating the flask were it was stored and then condensed with a heat exchanger before pouring the condensed liquid into a new flask. The temperature of the boiling vapors was measured before entering the heat exchanger. Different volumes were measured for a specified interval of temperatures to determine the amount of each fraction that was present in the bitumen. The mineral content of bituminous rocks after extraction were studied at apparatus X-ray phase analysis

The two kinds of bitumen as well as the two kinds of bitumen free sands were taken from Beke oil sands(no time to test Munaily Mola oil sands)

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2.4. Clay extraction. 70 g of the oil sands remaining after the extraction with chloroform were mixed with 200 ml of water to perform a simple stage extraction of the clay present in the oil sands . Since the clay is slightly soluble in water (due to the hydrogen bonds between the oxygen of the silicates and the hydrogen of the molecules of water ) the insoluble sands would not dissolve and the clay will form a solution with the distilled water used. After mixing the distilled water and the sand properly, a filtration was made to separate the suspended insoluble materials of the water, collecting the solution of water and clay in a flask. A simple funnel and filter paper was used for the filtration and the filtrate was collected into an Erlenmeyer flask. The solution of water obtained( the filtrate) was first boiled with a heater during 2 hours and then poured into a Petri dish that was put into an oven to remove all the water. Possible errors, the retained solution of the remaining sands after the extraction with water has the same concentration of clay as the solution filtered before, but no washing of the refines was performed because the amount of retained solution was very small and the amount of clay in that solution was considered negligible. The absorption of solution by the filter paper also retains some clay inside it.

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2.5. Elemental Analysis. Clay extracted from Beke oil sands was ground in a mortar and put into some sample tubes to be sent to a special lab for the elemental analysis. Not much more information can be given in this section because the experiment was not performed by the reporter. However, the results of the experiment will be shown and discussed in the results and discussion section. 2.6.Microscopic Analysis. Munaily mola oil sands and Beke oil sands were put into some sample flasks as well as some bitumen and extracted oil sands from the extraction with chloroform. As in the elemental analysis, the samples were sent to another lab to be analyzed. The results will be shown and discussed in the next section.

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3. Results and discussion. In this section the results will be shown and discussed and the experimental problems will be treated . 3.1. Extraction with chloroform. The mass of the filter paper used to wrap the oil sands was 11.62 g and the mass of the oil sands with the filter paper was 235.39 g. After the extraction the mass of the Petri dishes used to weight the sands was 325.99 g and the mass of oil sands processed was 180.76 g. Besides, the filter paper after the extraction was weighted again and its mass resulted to be 12.51 g. The mass of the oil sands used in this experiment can be calculated just deducting the mass of the filter paper from the mass of the unprocessed wrapped oil sands. The mass of the oil sands before the extraction is: To the mass of the sands after extraction should be added the extra mass that the filter paper got after the process. With that, and the mass of the untreated ore ( already obtained), it is easy to estimate a percentage of bitumen in natural oil sands from Munaily Mola deposit. The total mass of the treated oil sands was : The mass of oil extracted was then: and the fraction of bitumen in the natural ore was calculated by the following way:

The mass of the dried sands with the Petri dishes was 506.41g and the mass of the dried sands was . The amount of water was the mass of oil sands after the extraction minus the mass of the dried sands: . and its

fraction was : The total mass of dried sands in the sample was then:

Bitumen fraction=NaturaloremassTreatedoremass

Naturaloremass=

223.77181.65223.77

=0.188230.19

235.3911.62=223.77 g

506.41325.99=180.42g

180.76180.42=0.34 g

0.34

223.77=0.00152

223.77181.65=42.12g

180.76+(12.5111.62)=181.65g

181.650.34=181.31 g

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The following table gathers all these results together:

Table 3.1 Sum up of the results obtained in the extraction with chloroform.

Mass (g) Fraction Percentage

Bitumen 41.12 0.18823 18.82%

Sand 181.31 0.81025 81.03%

Water 0.34 0.00152 0.152%

Mass of the oil sands = 223.77 g

The sum of the mass of the bitumen, sand and water may not be the whole mass of the oil sands processed ( 223.77) due to weight mistakes and, when the sands were unwrapped after the extraction some of them may have been lost ( approximately 1 g). It is easy to see that the fraction of bitumen is quite high, with almost a 19% of bitumen and a very small amount of water in Munaily Mola oil sands. The dried sands are more than the 81% of the mass , however, in the next sections a deeper look is going to be made into these sands to understand them better.

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3.2. Thermo-contact method. For Munaily Mola oil sands at a maximum temperature of 450C during 45 min inside the reactor, the mass inside it was 336.71g and the product was poured in an Erlenmeyer flask of 113.57 g. The mass of the product (with the flask) was 156.59 g and the mass of oil in the flask was . With the previous data , the percentage of organic substances into the oil sands was :

13%.

The second thermo-contact method was performed during 60 min at a maximum temperature of 450C. The mass of oil sands put into the reactor was 401.35 g and the mass of the flask where the product was poured was 85.98 g. The mass of the product after the second thermo-contact method was 119.61 g (with the flask) and the mass of oil was .With those data, the percentage of the organic substances into the oil sands was calculated to be 8.4 % . Here, not all the oil sands put into the reactor suffered a transformation. This is because a part of them remained beyond the reach of the heat. Besides, formation of coke was observed. Finally, the last thermo-contact method was performed during 45 minutes at a maximum temperature of 550C . The mass of oil sands put into the reactor 292.42 g and the mass of the flask where the product was poured was 85.93 g. Paraffins are observed to appear like white pellets into the condensed stream of the heat exchanger. The mass of the product after the second thermo-contact method was 119.48 g ( with the flask) and the mass of product was .The percentage of the organic substances into the oil sands is:

11.5%

156.59113.57=43.02g

43.02g

336.71 g=0.12780.13

119.6185.98=33.63 g

33.63g

401.35g=0.084

119.4885.93=33.55 g

33.55 g

292.42 g=0.1147

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It was supposed to be final thermo-contact method for 60 minutes and a maximum temperature of 550C but due to experimental problems it was not performed.

After those experiments, Beke oil sands were taken to repeat the process. 395.52 g of sands were put inside the thermo-contact basin and the mass of the Erlenmeyer flask for pouring the product was 94.79 g . The first process was hold for 45 minutes at a maximum temperature of 450C. The mass of the product ( with the flask ) was 116.04 g and the mass of product was calculated to be : The percentage of oil in the sands was then calculated : However, the 45 minutes were not enough for the sands to release all the oil so, after that, the same oil sands were put into the reactor again to release all the organic materials obtaining new product that was poured with oil obtained before. Its final weight ( with the flask ) was 116.56 g and mass of the product was calculated to be So a true percentage of oil into the sands was calculated again:

5.5%.

A second experiment was performed for 60 minutes and a maximum temperature of 550C. The mass of the flask used for storing the product was 98,28g and the amount of oil sands put into the reaction basin was 466.42 g. The mass of the product obtained ( with the flask) was 117.69 g and the mass of product obtained was determined to be . With these results the percentage of oil into the sands processed was calculated:

4.16%.

116.0494.79=21.25 g21.25 g

395.52 g=0.05373

116.594.79=21.77g.

21.77 g

395.52 g=0.055

117.6998.28=19.41g

19.41g

466.42g=0.0416

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107.2384.34=22.89g

22.89g

469.51g=0.0488

Then, the next experiment was executed at a maximum temperature of 550C and during 45 minutes. The mass of the Erlenmeyer flask for keeping the product was 113.56 g and the mass of sands inserted into the reactor was 491.88 g. This time, a coverage was put between the heat exchanger and the flask to avoid big losses of vapor. However the 45 minutes were not enough to achieve such a high temperature so the experiment was carried on for 30 more minutes. The mass of the product obtained(including the flask) was 140.59 g and the mass of oil obtained was .This information leads to a yield of : 5.5%. A final experiment was performed with Beke oil sands at a maximum temperature of 550C and during 60 minutes. The mass of the flask where the condensed product was going to be stored was 84.34 g and the mass of sands put into the reactor was 469.51 g. The same coverage was used to avoid the escape of non condensed fractions. However, during the hour of the experiment, the reactor did not have time enough to achieve the 550C . So, after weighting the mass of the product after the 60 minutes, the experiment was continued until the temperature desired was reached. After the 60 minutes, the mass of the product and the flask was 107.23 g and the mass of the oil without taking into account the flask was

giving a yield of:

4.9%. When the final temperature of 550C was achieved the mass of the flask and the product was 108.17 g which implies that the mass of oil obtained was and the yield obtained was: 6.1%

140.59113.56=27.03 g

27.03g

491.88g=0.055

108.1784.34=23.83g

23.83g

469.51g=0.0614

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The results are gathered together in the next table.

Table 3.2 .Results from the thermo-contact experiments.

Time( min) Mass of oil sands (g) Mass of oil obtained(g) Oil fraction obtained

45 336.71 43.02 0.1278

Munaily Mola oil sands

Tmax =450 C

60 401.35 33.63 0.0840

45 292.42 33.55 0.1147

Munaily Mola oil sands

Tmax =550 C

60

45 395.52 21.77 0.0550

Beke oil sands

Tmax =450 C

60 466.42 19.41 0.0416

45 494.88 27.03 0.0550

Beke oil sands

Tmax =550 C

60 469.51 22.89 0.0488

During the process with Munaily Mola sands, the experiment was not performed adequately to determine the yield or the percentage of the organic fraction inside the oil sands due to the release of vapors before being condensed by some holes of the pipe that carried the stream from the reactor to the heat exchanger. Furthermore, the heat exchanger didn't have enough area for the exchange of heat and a big fraction of the stream left the equipment as vapor so that one was lost too. In the second experiment, it was observed the formation of coke. This might have been due to the high temperature so that heavy molecules began to break into smaller ones taking hydrogen from others producing coke.

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Apart from the vapor loses and experimental problems, the main problem was to determine the temperature inside the reactor, this is because the controller did not read the appropriate temperature and then it was impossible to know the temperature inside the basin. Besides, the paraffins seen in the last experiment with Munaily Mola sands were formed because they were condensed very fast in the heat exchanger and it was easy to see them. They were already being part of the bitumen. However, when testing the Beke oil sands, those experimental problems were avoided changing the heat exchanger and ensuring the joints between the reactor and the exchanger. Besides, for this kind of sands the reactor and its temperature controller were fixed so that the temperature displayed by the device was the true temperature inside the reaction basin so the value of the experiments with Beke oil sands was increased a lot. Unfortunately, the content of oil in the sands determined was much lower than expected so there might have been other mistakes that were not perceived like the loss of the lightest fractions of the bitumen that were not condensed into the heat exchanger. When the coverage was used in the last two experiments the percentage of oil determined into the sands increased a lot as well as the mass of hydrocarbons obtained with this method. Nevertheless, even with this increase in the hydrocarbons obtained it was not enough to reach the expectations of previous experience. From previous experience, it was known that the oil obtained from the thermo-contact method was a 16 % of the total mass introduced in the reactor for Munailly Mola oil sands and a 12% for Beke oil sands. As it is shown in the table 3.2 that fractions were not achieved, that a quite important amount of vapors were produced that could not be condensed and escaped out of the system. In the next figure another table, taking into account the previous problem is displayed.

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Table 3.3. Summary of all the results of the thermo-contact method.

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3.3.Fractional Analysis.[9,10] The results of the fractional composition of the bitumen obtained from the extraction method is shown in the next table:

Table 3.4.Fractional composition of organic part of extracted oil sands.

Composition PBR

Fractional composition, wt. %:

Boiling point 180

180-250

250-350 350- until end of boil

1,19

2,83

4,66

91,32

The results of the fractional composition of the mineral part after the extraction of the bitumen is shown in the next table: Table 3.5 Fractional composition of the mineral part of the extracted oil sands.

SiO2 -Quartz..79.1 %

NaAlSi3O8-Albite..11.8 %

KAlSi3O8 -Microcline9.0 %

Carbon. ..0.1%

The results of the fractional analysis of the bitumen obtained with thermo-contact method is presented in table 3.6:

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Table 3.6.Fractional composition of the bitumen obtained with the thermo-contact method.

Temperature(C) Fractional composition, (wt. %): .. 180

180 250C 250 3000 300 350

350 ..

7.9 12.2 12.6 52.6 14.8

(H,K AND K,K mean start of the boiling and end of the boiling of the organic mixture) The results of the fractional analysis of the mineral part of the oil sands treated with thermo-contact methods are shown in table 3.7. Table3.7. Fractional composition of the mineral part of Beke oil sands treated with the thermo-contact method.

Formula name Formula Quality Index

Quartz SiO2 0.675 Calcite CaCO3 1.129

Calcium Sulfide CaS 0.803 Calcium Oxide CaO 1.022

Portland Ca(OH)2 1.155 Graphite C 1.453

Looking at tables 3.5 and 3.6 it is easy to advert a big different in the amount of big and small molecules present in the bitumen. The cause of this difference is the thermal and catalytic breakdown of the molecules that is produced in the thermo-contact method. In the bitumen obtained from the extraction more than the 90% of the weight belong to large molecules in the last boiling interval. Very small percentages of light molecules are observed in the bitumen obtained by extraction.

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However, in the bitumen obtained with the thermal method, less than the 15% percent of the weight lies in the heaviest molecules and the lighter parts win importance. The bitumen in the oil sands used in the extraction and the thermal method is the same, but in the thermo-contact method the hydrocarbon chains are broken into smaller ones leading to this differences. When looking at the mineral part of the oil sands, no big differences are appreciated between the extracted sands and the thermal treated sands. Both of them are formed by quartz calcite and other components with a very similar composition. 3.4. Clay extraction. The dried clay from the Petri dish was put into a filter paper and then weighted, the mass of clay was 0.36 g , since the mass of dried and extracted oil sands was 70 g that leads to a fraction of The fraction of clay in the dried and free of oil sands is too small for the expectations got by previous experience. The retained solution of the remaining sands after the extraction with water has the same concentration of clay as the solution filtered before, but no washing of the refines was performed. That happened because the amount of retained solution was thought to be very small and the amount of clay in that solution considered negligible. However, that might have been the cause for getting such a low value in the fraction of clay. Besides, it must also be considered the absorption of solution by the filter paper that also retains some clay inside it.

0.36

70=0.005143

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3.5. Elemental Analysis.

The sample of clay was tested, giving the following results:

Sample:Clay

Element Concentration Intensity

Fe 0,349 3,95

K 1,270 2,26

Ca 60,304 255,13

S 29,799 17,78

Cl 3,987 2,24

P 3,773 1,09

Sr 0,329 3,85

Mn 0,189 1,58

It is easy to see that the clay is formed in a 90% by Calcium and Sulfur, but that it is not coherent with the chemical formula of the clay, which is Al2O3 2SiO2 H2O. The Calcium and the sulfur suggest that the chemical formula of the clay inside the oil sands from Beke is CaSO42H2O, which is the formula of the plaster. It must be said that Hydrogen and Oxygen are not detected by this method and the rest of the elements shown in the list belong to other molecules and substances that are mainly impurities and are present in a very small fraction. Although clay cannot be taken out of Beke oil sands the plaster that can be obtained can be useful for many applications, most of them medical but also for making pieces of art and many other practical uses.

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3.6.Microscopic Analysis. The results of the microscopic analysis showed some pictures of the clay (plaster ) , the oil, the extracted and dried oil sands and the oil sands from Beke and Munaily Mola. Oil:

Figure 3.1. Microscopic image of oil obtained from oil sands (150x)

In the figure 3.2 a continuous matrix of oil is shown with some dispersed black points. Those are small particles of oil sands that were entrained in the extraction, and crossed the filter paper with the chloroform and the oil. Diameters o less than 1 m are seen so it is reasonable to think that they were able to cross the cellulose grid of the filter paper.

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Clay:

Figure 3.2 Two images of clay took out of extracted and dried oil sands, one with 10x and another with 150x.

As it is shown in figure 3.3 the particle size of the clay is very varied and can be extremely small and quite big . The range is difficult to estimate but is obvious that is quite wide, the reason why that happens is that the clay was ground manually with a mortar. Dried and extracted sands: Figure 3.3. Microscopic view of bitumen and water free oil sands.(5x)

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Figure 3.4 shows a lot of bitumen free sand grains, however, some of them are quite black, that is because some bitumen remained attached to the grains through the pores . The particle size of the sand grains is about 0.5 mm although it varies a bit too. Oil sands:

Figure 3.4. Beke(left) and Munaily Mola ( right) oil sands microscopic photo (20x)

It is hard to say anything about the oil sands, the microscopic images do not actually explain a lot about them, basically it is shown sands covered with bitumen forming a kind of pulp. Te yellow particles that are shown in the figure are water, not pure water but a emulsion. In fact, in the interphase between the oil and the sand there is a small layer of water.

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4.Conclusions. As it was shown in this study, oil sands are mainly formed by a mineral part, the most abundant one and , in a lesser extent an organic part. The organic part is the one that is actually valuable and the challenge is to extract it with the cheapest and most environmentally friendly way. While the extraction with chloroform can give very high yields of extracted bitumen, the thermal method is faster and does not have the problem of using a dangerous and contaminant solvent. Besides, the thermo-contact method gives a lighter product more easy to refine and to transport via pipes. It was shown that Munaily Mola oil sands have a higher amount of bitumen inside them than the Beke ones (around 20%) . Although the mineral part of the oil sands are mainly useless ( due to the big amounts produced and the low demand of them) they have a small percentage of clay ( or plaster) that can be actually very useful for medical or building uses. The composition of the mineral part has been studied showing to be formed basically by quartz and other silicates while the clay inside that mineral part is actually plaster.

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5.Bibliography. [1] Fuel Chemistry Public Education . Research sequence: ( with Google as browser) Fuel Chemistry Public Education-Oil sands 10/07/2014 [2] de Malherbe R. , Doswell S. , Athanasios G.Mamalis de Malherbe M. "Synthetic Crude from oil sands" . 3rd Edition Dusseldorf 1983 pages 1-7 [3] http://en.tengrinews.kz/ Research sequence :(with Google as browser ) Tengrinews.kz - Tech-Science and Technologies-News Archive-8/7/2012-Kazakhstan will squeeze oil from sand and clay. 11/07/2014 [4] http://www.universalnewswires.com/ Research sequence:(with Google as browser) "Kazakhstan to begin work on oil sands in 2013, expert says". 11/07/2014 [5] http://www.capp.ca/ Research sequence : ( with Google as browser) www.capp.ca-Canada's Industry-Energy and Economy- What are oil sands? 11/07/2014 [6] http://www.ramp-alberta.org/ Research sequence: ( with Google as browser) www.ramp-alberta.org-Resources-oil sands-resource developement-in situ methods 11/07/2014 [7] Hooshiar A. Uhlik P. Liu Q. Etsell T. Ivey D. Fuel Processing Technology 94 (2012) 8085 [8] http://www.ramp-alberta.org/ Research sequence: ( with Google as browser) www.ramp-alberta.org-Resources-oil sands-resource developement-upgrading 11/07/2014 [9] AL-FARABI KAZAKH NATIONAL UNIVERSITY Faculty of Chemistry and Chemical Technology Department of Inorganic and General Chemistry Head of inorganic and general Chemistry Department, Dr. Niyazbayeva A.I. [10] , 2013

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Figure 1.2: Fuel Chemistry Public Education . Research sequence: ( with Google as browser) Fuel Chemistry Public Education-Oil sands 10/07/2014 Figure 1.3: Wikipedia.org Research sequence: ( using Google as browser) Oil sands (selecting the Wikipedia result.) 11/07/2014 Figure 1.5 Fuel Chemistry Public Education . Research sequence: ( with Google as browser) Fuel Chemistry Public Education-Oil sands 11/07/2014 Figure 1.7 de Malherbe R. , Doswell S. , Athanasios G.Mamalis de Malherbe M. "Synthetic Crude from oil sands" . 3rd Edition Dusseldorf 1983 pages 1-7 Figure 1.8 Ocon J. Tojo G. "Problemas de Ingeniera Qumica" Ed. Aguilar, volume 2. Figure 1.9 Wikipedia.org Research sequence :(with google as browser) Soxhlet apparatus 10/07/2014