Retorting Oil Shale by Microwave Power - American Chemical Society

19 Retorting Oil Shale by Microwave Power Ε. T. WALL, R. DAMRAUER, W. LUTZ, R. BIES, and M. CRANNEY

Downloaded by COLUMBIA UNIV on April 12, 2013 | http://pubs.acs.org Publication Date: June 1, 1979 | doi: 10.1021/ba-1979-0183.ch019

University of Colorado at Denver, 1100 14th St., Denver, CO 80202

Shale oil and a fuel gas have been produced by microwave -heating oil shale in a standard microwave oven in conjunc tion with experimentation to develop an in situ microwave retorting process. Various grades of oil shale have been subjected to high microwave fields. The derived oil has been submitted to various physical and chemical testing methods, and the chemical composition of the evolved gas has been evaluated. The specific gravity; pour point; yields of oil, water, gas, and losses; and spent shale are compared with parallel data obtained with the Fischer assay procedure. Important differences in oil flow properties and gas composition are discussed in view of microwave inter active theory.

shale represents an enormous reserve of fossil fuel for domestic and foreign needs (1,2). Shale oil production can be divided into direct and indirect heating processes (2). In direct heating, some of the products or some other fuel is combusted to raise the oil shale to the necessary temperature for conversion to gas and oil while an indirect process transfers heat from an outside source. Although high yields have been demonstrated in some indirect procedures (3), the application to in situ retorting has been limited. Direct processes developed for in situ recovery of shale oil have not demonstrated sufficient control of the under ground combustion for reliable operation. Electromagnetic radiation in the microwave frequency spectrum is absorbed most strongly by molecules with permanent dipole moments (4). The relaxation phenomenon of this absorbed power manifests itself in a heatlike reaction. The University of Colorado Oil Shale Project has studied the degradation of the liquid-fuel precursor (kerogen) by micro wave interaction. Kerogen is a moderately strong absorber of this radia0-8412-0468-3/79/33-183-329$05.00/0 © 1979 American Chemical Society

In Thermal Hydrocarbon Chemistry; Oblad, A., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1979.

330

THERMAL HYDROCARBON CHEMISTRY

tion because of its large percentage of polarized bonds and entrapped polar molecules (5). Microwave retorting represents a controllable underground application of energy without combustion. It is well known that important differences do occur with different methods of thermal retorting, and microwave interactive theory indicates even greater differences may be possible. We examined the products of this novel retorting system by using product quality as feedback control to gain some insight into the basic microwave interaction with fuel precursors.


Experimental Equipment. A commercial microwave unit ( rated at 2450 MHz and 650 W) was modified to fit a beaker-shaped quartz retort of approximately 500-mL capacity in which the oil snale was placed. Much effort was expended with this original design in obtaining materials, both of low microwave loss and high thermal stability. The apparatus was required to be gas tight. The oil and gas produced were fed through glass tubing to a series of condensers, a mercury manostat, stainless-steel bellows diaphragm pump, a gas test meter, and various gas collection apparatus (see Figure 1). The literature has virtually no references for using a commercial microwave oven unit for high temperature applications on a closed system. Each observation and parameter that changed gave important data and direction in designing a possible microwave interactive process. A quartz vessel was required because of its lower microwave energy absorption (7) and low reflectivity, a quality not well understood but well documented in our experiments. A newer apparatus, essentially a new cavity with greater loading and better reproducibility, is nearing completion. The experiment can be varied by changing the manner of collection of products, the atmosphere in the retort, and the sample size. A modified Fischer assay apparatus was obtained from the Colorado School of Mines Research Institute with the temperature program controlled manually with a chromel-alumel thermocouple readout. The signal from the thermocouple was monitored by a Radiometer pH/mV meter and outputed to a calibrated laboratory recorder. Gas collection was either metered or collected over water by using a mercury manostat instead of solenoids (6). Crude oil analysis techniques, developed by the Bureau of Mines (9), was used initially to describe the overall quality of the product. Spent shale samples were ashed using a two-day, low temperature procedure. The covered samples were placed in a room temperature furnace, and the temperature was increased to 700°C ( 3 7 0 ° C ) in a near-reductive atmosphere. The sample was uncovered and the temperature was increased to 7 5 0 ° F ( 3 0 0 ° C ) for one more day with air forced over the sample. This method has been suggested to cause the least changes to heat-sensitive mineral components of the shale (17). Actual experience has shown that the time for this procedure can be halved because of the porous nature of the spent shale and the small sample size. Results are presented as weight percent of the pre-retorted sample.



SAMPLE

MICROWAVE UNIT MERCURY MANOSTAT

S.S. DIAPHRAM PUMP

GAS COLLECTION ANALYSIS

Schematic of microwave retorting operation

CONDENSERS TRAPS

Figure 1.

GAS

PURGE

U-TUBE MANOMETER


•MASS S P E C .

• G.L.C.


332


The gaseous product was examined using a Perkin-Elmer 3920B programmed temperature chromatograph. Oxygen and nitrogen content were used as a leakage indicator, and the gas outputs were adjusted as to volume and energy content. Crude absorption measurements were made be measuring the temperature rise of known quantities of water and shale in a standard microwave oven. Although by no means an exhaustive study, this method allowed us to confirm the level of power consumption and its variation with kerogen content. Shale Samples. Initial experimentation was carried out on samples graciously supplied by TOSCO from their grounds located in Golden, Colorado. These samples assayed at 35 gal/ton by modified Fischer assay. These samples had been exposed to weathering for approximately 10 years. Results from these samples are examined in Tables I and VII. Samples of various grades were obtained from the vicinity of the large retort facility of the Laramie Energy Research Center and represented a loose collection of uncharacterized pieces of oil shale. Fischer assays were performed in this laboratory. Sample size ranged from 100 to 200 g, depending on specific gravity. Retorting Procedure. Oil shale of a block configuration with sides parallel to the bedding plane was halved with one piece retorted and the other ground for Fischer analysis of maximal oil content. Sharp projections of rock were removed, and the retort was centered in the cavity and sealed. The entire system is purged initially with nitrogen or helium to remove oxygen. Results reported here used no other atmosphere except that generated by the product evolution of the shale. A moderate vacuum of 60-80 mm Hg was maintained to prevent loss of product although samples run without vacuum were found not to differ significantly. As many as four traps were used for sample collection, with two circulating ice-water condensers, a high surface-area dry ice/acetone trap, and a 3 2 ° F ( 0 ° C ) condenser packed with glass wool being the final configuration. The unit is activated and the experiments are clocked with a built-in timer. Results and Discussion Microwave Power. Microwave heating has been examined with renewed interest since the development of ovens for the home and of high power, high efficiency industrial equipment. Microwave interaction has long been used to probe structural details of polymers (10) and rotational/vibrational spectra of small molecules. Higher power applications have become more prominent. In considering the mechanism of interaction of microwave energy and materials, a simplified model of a capacitor with the material between charged plates can illustrate the more important aspects of heating (4). The ability of the material to maintain the charge separation (that is, resist current flow) is closely related to the inverse of the dielectric constant ( e ' ) . When materials are subjected to the electric field between the plates, those with permanent dipoles (polar molecules) will orient



19.

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Microwave Retorting of Oil Shale

333

their partial positive charges toward the negative capacitor plate. This phenomenon is known as polarization. Polarization can be classified as electronic (electron cloud distortion), atomic, molecular, ionic, and crystalline. The point of maximum polariza tion in a system would occur when all dipoles reacted to the applied field and aligned. This is difficult to obtain even in a static situation. In an alternating field situation, the dielectric remains the same or decreases as the frequency increases past the microwave region (Ii). In the microwave region, attainment of equilibrium is more difficult, and there is an observ able lag in the dipole orientation which is commonly called relaxation. The polarization then acquires a component out of phase with the field thermal dissipation of some of the energy of the field. This dissipation and its relation to the normal charging current can be related by Equa tion 1 where e' is the measured dielectric constant of the material and e" , tan δ =

loss current c" , . r — — (!) charging current e is its loss factor. As the frequency approaches zero, c" approaches zero and e approaches the static dielectric constant (12). At very high fre quencies most of the polarization disappears. Small molecular polariza tions in a low viscosity medium would give a maximum near the microwave frequencies; large molecules with restricted orientation free dom would have maxima at frequencies lower than microwave. However, true resonance effects are not seen in impure or mixed materials. The behaviors of the dielectric constant and loss factor are often considered separately for a given material because usually only the loss constant changes dramatically in the microwave region (see Equation 2.) Hence the tan δ can approximate the loss behavior of similar materials (4,13). i X

-7-

€

" = ' tan δ €

(2)

Microwave heating has been called volume heating because of its frequent independence of thermal conduction. Penetration is inversely proportional to frequency and will be greatest with those materials of low loss (e.g., saturated hydrocarbons, some ceramics, glasses, etc.). Radiated heat from the surfaces of materials heated in microwave cavities can reach high internal temperatures. Low thermal conductivity samples can retain heat build-up until increased rotational freedom can be obtained and then can absorb power at a more rapid rate. Some materials heat so slowly by thermal conduction that only either size reduction or volume heating would be practical (14). Application to the fracturing of concrete by using broadcast microwave power takes advantage of the low thermal conductivity to concentrate heating interaction (4).



334


High polymers always have atomic and electronic polarization contributing to the dielectric constant. In heterogeneous materials, an additional type of polarization arises from an accumulation of charge between regions with differing loss characteristics. High polymers containing polar groups can show orientation polarization attributable to change in orientation of molecular segments in an externally applied field without changing the entire molecular orientation (10). Crosslinking of the polymer segments can reduce this freedom considerably. Pure rubber is a hydrocarbon with little polarity. When it is vulcanized, the reaction with sulfur gives crosslinking with a corresponding increase in dielectric constant attributable to polar carbon—sulfur bonds. However, as crosslinking increases, the rotational freedom is restricted and the dielectric constant decreases. Here also, interfacial polarization contributes to the overall loss (10). Results from Microwave Shale. From the preceding discussion, oil shale would offer an interesting substrate for microwave power interaction. Kerogen is chemically composed of many segments with permanent dipoles and contains entrapped polar compounds (5,15). Although a solid, its heterogeneity would be expected to and did display a liquidlike dielectric constant and suitable loss tangent. Also, its layered structure in the shale would have a high interfacial polarization contributing to power absorption. Early experimentation showed that the rock strata, devoid of organic matter, had very little power absorption properties (14), and a sequential heating situation was envisioned and demonstrated. That is, the initial fixed water is heated, the fracturing of the shale is followed by kerogen pyrolysis, and lastly, the spent ore absorbs power. This selective interaction indicated lower power requirements than a strictly thermal process. After a period of time (depending on sample load), water vapor condenses in the first traps, accompanied by major cracks appearing parallel to the bedding plane. After the majority of the water vapor condenses, sulfurous gases appear, followed by oil vapor and mist, all continuing to completion. The spent shale remains solid but with much less structural integrity and with serious fracturing along planes parallel to the bedding plane, together with many small cracks greatly increasing the shale porosity. Gas output was copious, often overloading condensing and separating systems. Also, loading of the solid shale indicated a minimum weight below which coupling with the microwave energy was ineffective. Mist formation exceeds the nominal 3%-5% reported in the literature for many processes (8). Nucleation methods have not been attempted. Since gas evolution was quite copious, it was assumed that it contained a large proportion of the overall heating value of the products. This was later confirmed. Also, because of the closed system, no


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dilution of the gas occurred, and the calorific heating value should be higher than most direct heating processes. Table I lists some results of microwaving oil shale (35 gal/ton) from TOSCO. These initial experiments indicated a need for comparative studies with thermally produced liquid and gaseous products. Flow property indicators (API gravity, pour point), showed conflicting trends. The gas output was very high. Studies of oil generation and degradation with thermal heating have led to a simplified mechanism for the estimation of retort products of blocks of shale (15). Experimental data showed that the highest oil yields were obtained by removing intraparticle oil [(Oil) , Figure 2] very quickly either by increased heating rate, as in Fischer assay, or by using a sweep gas; i.e. k > > fc , the rate constants for intraparticle oil production and degradation by coking, respectively. Since coking has been described as the main degradation mechanism of shale oil by thermal heating, and since microwave retorting under these conditions produces low residual carbon, cracking reactions would more easily describe the increased gas production by microwave retorting. The effective gas and oil production rate in microwave retorting is so rapid that cracking reactions must occur inside the shale as soon as oil liquid is produced (microwave interaction is greatly decreased in gas phase reactions). Frequently the inside of the blocks of spent shale are devoid of visual carbon.


IP

c

d

Table I.

Initial Results on Retorting Oil Shale by Microwave Power Parameter

Results

Gas and losses Carbon in semicoke Oil yield Heat of combustion API gravity (pour point 3 0 ° F ) Nitrogen Sulfur Conradson coke Ash

21.0 (%) 4.5 (% of spent shale weight) 71.0 (% of Fischer Assay) 16,744 (Btu/lb) 17.2 1.9 (%) 0.93 (%) 5.5 (%) 0.3 (%)

(KEROGEN - BITUMEN)

^

> (01L) + CARBONACEOUS RESIDUE + GAS |p

(k, + k ) g

COKE + GAS

OIL

PRODUCED lOth Oil Shale Symposium Proceedings

Figure 2.

Simplified mechanism for oil production (15)



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Results from a series of experiments performed under maximal energy absorption conditions are shown in Table II. These samples were subjected to a microwave field until gas and vapor evolution returned to near background. These conditions are not those of maximal efficiency either in power used or in yield obtained, but do show a direct comparison with a thermal retorting system, the modified Fischer assay being an "indirect process" reference. The microwave run was complete within 30 min since dependence on heat transfer, as in the thermal retort, is unnecessary. Comparing some characteristics of the oils obtained, significant differences in the overall specific gravity and in the pour points were observed. The Fischer assay specific gravity decrease correlated well with increasing yield, as is often the case in the literature. In all cases, the specific gravity of the microwaved oil is higher than the Fischer assay oil; this held true for every sample tested. Yet, the microwave oils show excellent flow properties which were later confirmed by kinematic viscosity measurements. The trend for greatest pour-point depression seems to be in the area of middle grade of Colorado oil shale. It has been noted that shale oil properties can vary with the percentage yield of a thermal process. The percentage of oil recovery compared with the Fischer assay is presented in Table III, which shows some more characteristics of the retorting runs of Table II. The data

Table II. Characteristics of Microwave-Produced Oil and Oil from the Modified Fischer Assay of Divided Oil Shale Samples Number of ExperiGrade merits (gal/ton) 68.8 40.6 23.0 12.5

Microwave Oil

Fischer Assay Oil Specific Gravity

Pour Point (°F)

Specific Gravity

Pour Point (°F)

0.896 0.917 0.926 0.950

53 69 53 60

0.956 0.934 0.937 0.940

45 10 19 37

Retorting Oil Shale by Microwave Power - American Chemical Society

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