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Characterizing of oil shale pyrolysis process with laser ultrasonic detection ZhiQing Lu, Xiaoquan Hai, Jianxin Wei, and Rima Bao Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.6b01590 • Publication Date (Web): 17 Aug 2016 Downloaded from http://pubs.acs.org on August 17, 2016
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Characterizing of oil shale pyrolysis process with laser
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ultrasonic detection
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Zhi Q. Lu,a, b, *, Xiao Q. Haia, b, Jian X. Weia, Ri M. Baob
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a
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Petroleum, Beijing 102249, China
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b
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University of Petroleum, Beijing 102249, China
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Abstract
State Key Laboratory of Petroleum Resources and Prospecting, China University of
Beijing Key Laboratory of Optical Detection Technology for Oil and Gas, China
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Laser ultrasonic was proposed to characterize the porolysis process of the oil
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shale. The ultrasonic velocity was produced by a non-contact all-optical method in the
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three regions of Barkol, Yaojie, and Longkou of China. It was found that the
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ultrasonic velocity was related with the pyrolysis temperature of the oil shale. The
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pyrolysis process was divided into three stages due to the ultrasonic propagation
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speed in the oil shale. The ultrasonic velocity had small changes from 20 °C to 320 °C
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in the first stage, and a sharp decline between 320 °C and 470 °C in the second stage,
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until another small change above 470 °C in the third stage. The variation of the
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velocity was qualitatively explained, which was considered to be closely related with
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the characteristics of pyrolysis process in oil shale. An empirical equation of the
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velocity attenuation equation was proposed to estimate the beginning and the end of
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the decomposition of the kerogen. It is a new way to characterize the process of the
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pyrolysis of oil shale by using the laser ultrasonic.
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■ INTRODUCTION Oil shale, a sedimentary rock considered as a predominant alternative source 1
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for alleviating the pressure of petroleum supplies, contains minerals, kerogen, and
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bitumen.1 Oil shale has been used for retorting to yield shale oil and burning directly
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as a fuel to generate electricity or heat for many years. Kerogen is considered as the
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main organic matter in oil shale yielding a significant amount of oil through pyrolysis,
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which is one kind of oil shale thermochemical conversion technologies, involving the
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thermal degradation of virgin material resulting in the production of gas, liquid and
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solid.2 For exploring the optimal operate conditions, many researchers have embarked
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on the process of pyrolysis of oil shale, and many works have been done about the
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influences of major parameters including the pyrolysis temperature, heating rate,
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residence time, pyrolysis atmosphere, operating pressure, as well as the particle size,
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density, and inorganic matter content of oil shale.3-17 Thermal analysis is commonly
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employed in the process of pyrolysis of oil shale, which focus on the thermodynamic
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parameters or physical parameters change with temperature.18 For example,
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thermogravimetry is used to assess the mass loss of a sample as a function of
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temperature or time.19 Differential thermal analysis and differential scanning
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calorimetry are used to characterize fossil fuels during pyrolysis. So the thermal
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dynamic parameters based on pyrolysis experiments are vital in the evaluation of oil
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shale. In addition, some indirect methods have been developed, such as well-logging,
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x-ray diffraction and nuclear magnetic resonance spectroscopy etc.20-25
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Laser ultrasonic technology, with ultrasonic excited by pulsed laser and
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received by optical method, is currently one of hot topics in the field of the
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nondestructive testing and evaluation of materials.26-28 This technology has been
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applied in many fields, such as aerospace, microelectronics, biology and medicine etc.,
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with its advantages of non-contact, long distance, high spatial and temporal resolution
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and no environmental requirements. In recent years laser ultrasonic technology in oil 2
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field application also draw researchers’ attention. The longitudinal wave (P-wave)
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anisotropy in core shale was measured with laser ultrasonic. The measured velocities
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showed the significant relevance with the anisotropy of the core shale and provided
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detail information on the rock’s elastic constants, showing the advantage of laser
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ultrasonic than traditional transducer.29 Laser ultrasonic can be also used in the liquid
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of oil-water mixture to detect the water content. The ultrasonic P-wave velocity
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acquired by this method was found to be accelerated with the increase of water
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content. Different P-wave velocity corresponding to the different water content that
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can be used for detecting the crude moisture from 0% to 100%.30
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The present work focused on the P-wave velocity measurements in the pyrolysis
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process of oil shales by using laser ultrasonic technology as an all-optical method.
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Laser ultrasonic testing system was set up and the P-wave velocities corresponding to
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the pyrolysis of the oil shale were acquired and analyzed. The good correlation of the
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ultrasonic velocity with the temperature of oil shale pyrolysis indicates the possibility
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of the laser ultrasonic to be a new elevation in oil field.
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■ EXPERIMENTAL SECTION
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The sketch of the laser ultrasonic testing system was shown in Figure 1. When
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the short-pulse laser of 1053 nm irradiated on the sample surface, part of that energy
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is absorbed and the ultrasonic was produced in the sample due to thermoelastic
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mechanism. The ultrasonic was received by the interferometer on the other side of the
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sample based on photorefractive two-wave mixing. The resulted waveform was
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recorded by the digital oscilloscope and input into the computer to further processing.
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In the experiment the ultrasonic P-wave was recorded which is the first significant
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peak appears on the interferometer. The laser ultrasonic velocity data of the samples
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was determined by the time that the ultrasound waves take to pass through the sample. 3
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The oil shale used in this work were taken from three regions of China,
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Kazakhstan Barkol County in Xinjiang, Yaojie Street in Lanzhou and Longkou City in
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Shandong. The oil shale samples of Barkol, Yaojie and Longkou in the experiment
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were 25×25 mm2 after cutting and grinding, with the thickness of 3.30, 2.22, and 1.84
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mm respectively. Considering the anisotropy of the rock and the consistency of the
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experimental conditions, all the samples were cut parallel to the bedding plane of the
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oil shale. The first laser ultrasonic test of the samples was taken at room temperature
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before heated. Then they were heated from room temperature (20 °C) to 670°C under
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a vacuum condition with the temperature interval of 30 °C and the heating rate of 10
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°C/min, keeping 30 minutes at each temperature point. After each heating, laser
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ultrasonic tests were performed and the weight of the samples were recorded.
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■ RESULTS AND DISCUSSION
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The corresponding travel-time of the oil shale samples under room temperature
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was shown in Figure 2. A peak picking program has been designed that locates the
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time of the first peak. The take-off line was marked in Figure 2. The baseline indicates
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the delay time of 4.43 µs. So the travel time ∆t of the ultrasonic wave through the
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samples of Barkol, Yaojie and Longkou is 0.69, 0.89 and 1.62 µs, respectively. Then
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the propagation speed v of the ultrasonic wave is 2667, 2494 and 2037 m/s,
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respectively, which can be calculated by the travel time ∆t as a result of
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v = d /∆t
(1),
where d is the thickness of oil shale sample.
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The curves of the propagation velocity of ultrasonic wave in three samples with
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the pyrolysis temperature were represented in Figure 3 where the velocity decreased 4
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and appeared three stages with the rise of pyrolysis temperature. The raw ultrasonic
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data of the three samples were listed in Figure 3(a), 3(b) and 3(c) to show the velocity
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change with several pyrolysis temperatures of 20 °C, 120 °C, 300 °C, 360 °C, 390 °C,
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470 °C, 520 °C and 570 °C, respectively. Take the oil shale sample in Barkol as an
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example, the travel time ∆t read in Figure 3 (a) was 0.69, 0.68, 0.69, 1.21, 1.29, 1.61,
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2.21 and 2.25 µs, respectively. The corresponding velocity can be calculated by the
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formula (1) to be 2667, 2705, 2667, 1521, 1426, 1143, 832, and 818 m/s. As received
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in Figure 3(d), the propagation velocity of the oil shale sample in Barkol changed
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slightly from the beginning of the pyrolysis to ~ 320 °C. Then the propagation
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velocity had a sharp change from 2745.86 m/s at 320 °C to 1054.95 m/s at 470 °C.
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And then the velocity maintains small changes about 200 m/s. The change was well
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verified by the other two samples from Yaojie and Longkou in Figure 3(b) and 3(c)
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that the three oil shale samples present the same change in the process of pyrolysis
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with their different beginning velocity. The mass variation of the samples in
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temperature ranges from 20 to 600 °C was plotted in Figure 4. The mass loss is
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approximately16.5%, 40.9% and 26.7% for the three samples of Barkol, Yaojie, and
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Longkou, respectively. The difference of the mass variation related with their
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difference composition, origin, and their oil yield of 5.66%, 9.05%, and 14.16%,
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respectively.
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The variation of the ultrasonic velocity and the mass of the samples in Figures 3
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and 4 were considered to be closely related with the oil shale pyrolysis process.
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Below 300 °C, the mass variation is mainly caused by the release of the adsorbed gas
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and the water loss, including the gasification or volatilization of the pore water, 5
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on-site water and layer structure water in the oil shale. A series of physical reactions
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occurred at this stage such as the soft of hard shale particles and recombination
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between molecules, which also cause some mass loss.31 The ultrasonic velocities
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maintain small variation because the homogeneity of the sample was not destroyed
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below 300 °C .
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The great changes in velocity between 320 and 470 °C was attributed to the
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decomposition of organic matter in the oil shale samples, which was the main stage
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for releasing hydrocarbons. The decomposition of the kerogen mainly occurred
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between 300 and 500 °C. When the temperature reached 320 °C, kerogen in the
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samples began to decompose to produce combustible gas and shale oil, which
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volatilized at high temperature, resulting in most weightlessness of three samples
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about 9.3%, 25.3% and13.3%. In addition, porosities in oil shales have a significant
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impact on the ultrasonic velocity. The pores and the micro cracks in the oil shale have
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a random disordered distribution at room temperature. They increase gradually with
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the rise of temperature, but not obviously. When the kerogen in samples decomposed
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from solid to liquid or gas above 300 °C, the pores and the cracks increased quickly
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with inflation and connection, resulted large variation of density and internal structure
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of the samples32,
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changes correspondingly, appearing a sharp curve slope in Figure 3(d).
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. So the ultrasonic velocities through the samples have great
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The ultrasonic velocity has a significant slowdown after the temperature higher
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than 470 °C. The pyrolysis of kerogen was basically complete at the time and the
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pores and cracks in the samples increased little. The mass loss at this stage is mainly
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because of the thermal decomposition of clay and carbonate minerals with the release
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of CO2.18. The surface roughness and the shape of the samples were not affected by
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the high temperature in the pyrolysis progress. But the surface color now is taupe, and 6
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different from its original bright-black. Such change of the samples didn’t influence
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the measurement results. Figure 5 was plotted to further understand the variation of
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the ultrasonic velocity in the process of the pyrolysis. The velocity didn’t show linear
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change with the mass percentage of the sample, which indicate that the organic matter
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in the oil shale samples was not the only cause of the velocity change. The variation
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of the rock structure, such as the generation and restructuring of the pores and
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fractures, has great influence on the spread of the ultrasonic wave in oil shale.
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Combining the experimental results of the velocity variation with the
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temperature and the mass of the samples, a preliminary exploration of the velocity
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attenuation (VD) equation was proposed to estimate the pyrolysis process.
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VD = 1 −
V p2 V p20
(2)
× 100 %
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where Vp is the ultrasonic velocity in the sample at any time during the pyrolysis, and
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Vp0 is the velocity before the pyrolysis. The velocity attenuation with the pyrolysis
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temperature in Figure 6 shows clear stage change in the pyrolysis process. Two
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parameters were chosen to indicate the beginning and the end of the pyrolysis, as
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shown Figure 6. When the VD is ~10%, it is considered the beginning of the
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decomposition of the kerogen. And the VD is ~90%, it is considered the end of the
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decomposition.
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The pyrolysis of oil shale is a very complicated process, accompanied by a
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variety of complex chemical and physical reactions. The factors that influence the
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ultrasonic velocities are many and intricacy. Here the ultrasonic velocities were only
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measured and analyzed qualitatively. Its mechanism is not very clear and need further
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detailed research. The empirical equation of velocity attenuation from the three
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samples also need verified and corrected in further research. But this non-contacting 7
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optical method of laser ultrasonic provides us a new way to characterize and
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evaluation the pyrolysis process of oil shale.
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■ CONCLUSION
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In this paper, a non-contacting optical method was proposed for characterizing
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the process of the pyrolysis of the oil shale. The ultrasonic P-wave velocity acquired
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by this method was found to be interrelated with the pyrolysis temperate of the oil
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shale. The pyrolysis process was divided into three stages based on the propagation
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speed of ultrasound in the oil shale. Each stage was analyzed qualitatively combining
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with the characteristics of the pyrolysis and the variation of the ultrasonic wave
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velocity in oil shale. An empirical equation based on the pyrolysis characteristics of
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the three samples was proposed to estimate the beginning and the end of the
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decomposition of the kerogen. The present results show a new way to characterize the
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process of the pyrolysis of oil shale by using the laser ultrasonic as a non-contact
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optical method.
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■ AUTHOR INFORMATION
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Corresponding Author
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*Telephone: +86-13521209760. E-mail:
[email protected].
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Notes
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The authors declare no competing financial interest
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■ ACKNOWLEDGMENTS
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This work was supported by the Specially Funded Program on National Key
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Scientific Instruments and Equipment Development (Grant No. 2012YQ140005), the
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National Key Basic Research Program of China (Grant No. 2014CB744302), and the
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Excellent Young Teachers Program of China University of Petroleum (ZX20150108). 8
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The authors thank CNPC Key Laboratory of Geophysics for providing laser ultrasonic
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experimental conditions. Z. Q. Lu and X. Q. Hai contributed equally to this work
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herein.
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■
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Figure 1. The sketch of the laser ultrasonic testing system.
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Figure 2. The travel-time of the oil shale samples under room temperature.
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Figure 3. The raw ultrasonic data of the several selected pyrolysis temperature in the sample of (a) Barkol, (b) Yaojie and (c) Longkou. (d) The ultrasonic propagation speed with the pyrolysis temperature of the three samples.
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Figure 4. Mass variation of the different pyrolysis temperature of three different areas.
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Figure 5. The ultrasonic velocity with the mass percentage of the three samples.
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Figure 6. The velocity attenuation (VD) with the pyrolysis temperature of the three samples.
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