Article pubs.acs.

org/EF

Colloidal Petcoke-in-Water Suspensions as Fuels for Power Generation

Gustavo A. Nunez, Mara I. Briceno,*, Cebers Gomez, Takeshi Asa, Hamid Farzan, Shengteng Hu, and Daniel D. Joseph

Nano Dispersions Technology, Incorporated, Building 231, City of Knowledge, Clayton, Panama Babcock and Wilcox Power Generation Group, 180 van Buren Avenue, Barberton, Ohio 44203, United States Department of Aerospace Engineering and Mechanics, University of Minnesota, Minneapolis, Minnesota 55455, United States ABSTRACT: In this work, it is shown that, despite the low reactivity of petroleum coke (petcoke) and the presence of 40% water, a petcoke suspension having a large colloidal population burned with unprecedented high eciencies (>99%) without a support fuel. This paper is an account of the main combustion test results, obtained in a 6330 MJ/h pilot-scale boiler simulator located at the Babcock and Wilcox Research Center. This pilot plant simulates a full-scale utility boiler in many key aspects. Combustion tests of a typical heavy fuel oil (HFO) were carried out to produce baseline data for comparison to the colloidal petcoke in water suspension (CPW) performance. The CPW fuel showed, besides high particle reactivity during combustion, some advantageous characteristics, such as ease of pumping, metering, and atomization at room temperature, using conventional equipment designed to handle and re HFO.

1. INTRODUCTION Heavy fuel oil (HFO) is still used worldwide in industrial and power-generating boilers, including facilities in the east and west coasts of the U.S., where fuel oil can be conveniently shipped in oil tankers. However, with the rising price of oil and its attached fuel oil price, it has become necessary to nd less costly alternatives to keep the operational costs of any plant at competitive levels. Some alternatives, such as coal and petroleum coke (petcoke), are quite obvious given their comparatively historical lower cost and wide availability. Some of the shortcomings of burning pulverized fuels in oil-ring boilers can be overcome by preparing mixtures of the solid material with water or oil. This is not a new idea, and back in the 1970s and 1980s, there was intensive research and development on coalwater slurry (CWS) or coaloil slurry (COS).1 However, the interest in this kind of fuel came to an end in the U.S., mostly because of economic hurdles associated with low oil prices prevalent through the 1990s. Nonetheless, to the authors knowledge, there was no attempt to prepare petcoke in water slurries for use as the sole fuel in conventional boilers. At present, the oil price is increasing, and a denite higher price horizon is foreseen as new large consuming economies, such as China and India, become stronger buyers of fossil fuels. This situation is again becoming a driver to improve coal quality through cleaning procedures and more ecient combustion processes for the aforementioned technologies.1,2 Our research group has taken a new approach that deals with several of the limitations of CWS fuels, by means of the manufacturing of a mostly colloidal suspension of petcoke particles dispersed in water. The latter characteristic makes a great dierence regarding fuel reactivity and stability. Colloidal particles have a total surface area many times higher than the particles present on conventional CWS. Chemical reactions, such as oxidation (combustion) or sulfation, occur on the
XXXX American Chemical Society

surface of solid fuels or minerals. Large increases in surface area imply higher reaction eciencies.36 A second and also important aspect is the eect of particle size reduction in suspension stability. Increasing the colloidal fraction slows or prevents altogether sedimentation,3,5 one of the main bottlenecks of CWS in the past. In a previous paper,3 we presented the results of the preparation and combustion characteristics of a colloidal coalin-water suspension used as a reburn fuel. As expected, the colloidal nature of the fuel greatly improved the reburn performance, outdoing a higher rank pulverized coal and, under some operational conditions, approaching natural gas behavior in the same conditions.3 In this work, we present the combustion results of a colloidal petcoke in water suspension (CPW) used as the sole fuel in a small boiler simulator. The fuel was prepared in a similar way as the coal suspension described in our previous publication.3 Petcoke usually has an ash content lower than 1%. A fuel having less than 1% ash could be red, in principle, in a boiler designed for HFO, as long as the fuel has combustion characteristics similar to or better than fuel oil. However, ring only petcoke is next to impossible in most conventional boilers, without co-ring with a suitable (supporting) fuel. This fact is attributable to the low reactivity of petcoke related to the low volatile content, which is inferior to most commercial coals. Nonetheless, petcoke is an attractive fuel from the point of view of its cost per heat value (BTU) and from its market availability, although its combustion characteristics have relegated it to mostly being red in cement furnaces, uidized beds, and other specially designed boilers or being co-red with other fuels.
Received: July 26, 2012 Revised: October 23, 2012

dx.doi.org/10.1021/ef301249q | Energy Fuels XXXX, XXX, XXXXXX

Energy & Fuels This paper is an account of the main combustion test results, obtained in the 6330 MJ/h pilot-scale small boiler simulator II (SBS-II) located at the Babcock and Wilcox Research Center (BWRC), at Barberton, OH. The SBS-II tests simulated a fullscale utility boiler in many key aspects, such as ame stability, combustion eciency, and furnace and convection pass heattransfer characteristics under various operating conditions. It also included assessing emission characteristics of CPW combustion, including CO and NOx, which are highly dependent upon combustion parameters, such as in-ame oxygen availability, fuelair mixing, the nitrogen content of fuel, and other factors. For this purpose, about 3000 gallons of CPW fuel were manufactured in a pilot plant in a semi-batch fashion. Combustion tests of a typical HFO were carried out to produce baseline data for comparison to the CPW performance. The main purpose of these tests was to collect relevant and scalable data for commercial power generation.

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2. EXPERIMENTAL SECTION
2.1. Fuel Preparation and Handling. The petcoke was supplied by DTE Energy Services (Vicksburg, Mississippi) and previously milled to 200 mesh. Table 1 shows some of the most relevant properties of this fuel-grade petcoke sample.

Table 1. Physical Properties of Fuel-Grade Pulverized Petcokea

petcoke properties carbon (%) hydrogen (%) sulfur (%) vanadium (ppm) volatiles (%) moisture (%) high heating value (Btu/lb) particle size (mesh)
a

typical values 86 3.5 6.5 <2400 713 <1 15000 200

Information provided by DTE.

evaporation. On average, the nal petcoke content in the suspension was about 62% (w/w). A total of 12 tons of CPW fuel were manufactured in this fashion and later shipped to BWRC facilities in standard 300 gallon intermediate bulk containers (IBCs). To follow-up the CPW properties during storage, a couple of samples were kept in one 10 gallon container and one 55 gallon drum. As mentioned above, more details on the preparation method and a description of the wetcomminution apparatus can be found elsewhere.3 2.2. Evaluation of the Physical Properties. During manufacture, the particle size distribution of the petcoke slurry (before wet comminution) and CPW was measured using a laser diraction apparatus made by Microtrac. The measurement procedure was as follows: A small portion of sample was dispersed in 10 mL of sodium polyphosphate (0.25%, w/w) and sodium lauryl sulfate (0.75%, w/w) solution. About a third of this suspension was poured into the Microtrac mixing tank before circulation through the measuring cell. It is worth mentioning that, while the dry petcoke and petcoke slurry were relatively easy to measure and results were quite reproducible, CPW particle size characterization was less reproducible. Wet-sieving the aforementioned solution in a 600-mesh standard sieve (20 m opening) was used to validate the Microtrac results, and it was found consistently that sieving gave way to less mass retention than the laser diraction apparatus, although the dierence was on the order of 2 or 3 mass % below 20 m. A gravimetric method was used to measure the water content; a weighed sample of slurry or CPW was placed in an oven and let to dry at 120 C for at least 6 h. After cooling, the dry sample was weighed and the amount of water lost during the tests would allow us to calculate the initial moisture content. A moisture analyzer made by Arizona Instruments, Computrac model, was used to measure the water content of CPW during the combustion tests. A Brookeld DV-II+ Pro viscometer, set with a RV3 spindle rotating at 100 rpm, was also used to monitor viscosity during the tests. The viscosity reading was made 10 s after the start of the spindles rotation. A KinexusPro rheometer, manufactured by Malvern, was used to obtain steady-state ow curves for the CPW. The measuring geometry was a parallel plate system, 40 mm in diameter and set to a 1 mm gap. The ultimate analysis and other relevant properties for both CPW and HFO fuels are shown in Table 2.

The manufacturing process was batch-like and would begin by the preparation of a pre-slurry made of petcoke and a surfactant mixture solution. Both phases, dry solid and surfactant solution, were combined by means of a turbine style mixer. The surfactants were required to both wet the particles and detach bubbles from the hydrophobic petcoke surface. In this sense, a nonylphenol ethoxylated (NPE) surfactant was used as a wetting agent [0.25% (w/w) based on dry petcoke], and a linear alcohol ethoxylated (LAE) surfactant was used as a defoamer [0.05% (w/w) based on dry petcoke]. These surfactants were selected after a screening of several commodity surfactants; the selection criteria were based on the required pre-slurry properties: viscosity below 1000 mPa s and no foam. The NPE surfactant was supplied by Oxiteno, and the LAE was supplied by Shell. Tap water was used to prepare the surfactant solution. The nal composition of each 250 kg pre-slurry batch was on average 61.5% petcoke. Increasing composition beyond 62% produced a viscous suspension (more than 1500 mPa s) that was not adequate for further processing. Each pre-slurry batch was pumped into a continuously stirred tank to avoid sedimentation that otherwise was very fast, taking less than 1 h to produce severe settling. Once a 750 kg load was completed, the pre-slurry was processed continuously using a wet-comminution apparatus (previously described in ref 3). The ow rate was 3 ton/h of pre-slurry, and the residence time in the device was 5 s. The temperature of the output uid went up to 60 C in steady-state conditions because of friction heating, and in consequence, the water content diminished slightly (less than 0.5%) because of partial
B

Table 2. Comparative Chemical and Physical Analyses of HFOa and CPWb

HFO carbon (wt %) hydrogen (wt %) nitrogen (wt %) oxygen (wt %) sulfur (wt %) moisture (wt %) ash (wt %) high heating value (Btu/lb) viscosity specic gravity at 15.5 C ash point (F)
a

CPW 51.6 2.10 1.20 0.81 3.90 40.15 0.24 9000 500900 cP at 21 C 1.21

87.84 9.70 0.37 0.00 1.92 0.10 0.031 18152 393 SFS at 50 C 1.107 221

HFO supplied by New Brunswick Power. bTest analysis carried out at BWRC Laboratories.

2.3. Combustion Tests. The rst objective of this work was to corroborate that increasing the colloidal size population would result in enhanced combustion properties. The second goal was to evaluate combustion and emission characteristics of CPW to provide relevant and scalable data that would demonstrate the feasibility of using CPW as a fuel for power generation stations. To accomplish these goals, we decided to do the necessary tests that would (i) demonstrate stable combustion using CPW fuel at full load (6300 MJ/h) without the use
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of any support fuel and (ii) compare CPW- to HFO-ring performance. In particular, the following tests were carried out: valuation of the CPW ame stability and shape under various operating conditions and estimation of combustion eciency, furnace, and convection pass heattransfer characteristics also under various operating conditions. CO and NOx emissions were characterized during the tests; these gases are closely related to combustion eciency (CO) and oxygen availability at the ame and ame temperature (NOx). 2.3.1. Description of the Combustion Facility. The so-called SBSII was used for the pilot-scale tests. This facility belongs to the BWRC and was contracted for this evaluation. The SBS-II is capable of ring gaseous, liquid, and pulverized solid fuels. It is a newly constructed and totally integrated facility for fuel evaluation, testing, and development of fossil fuel combustion hardware and emission control equipment, under commercially representative conditions. To carry out tests for CPW, the furnace was equipped with a single wall-red XCL low-NOx burner and one I-Jet atomizer. The existing 6330 MJ/h low-NOx XCL burner was modied to accommodate the atomizer positioned along its centerline. It operates on the principle of controlled mixing of the oxidizer and fuel to minimize NOx and unburned combustibles. Most of the combustion air was swirled by spin vanes inside the two concentric annuli. Burner vane adjustment was the primary way of adjusting near burner secondary air swirl, to control the fuelair mixing pattern. The latter was necessary to maintain ame stability and, at the same time, control NOx emissions. A small fraction of the combustion air was introduced into the central core zone, primarily for cooling purposes. The burner was comprised of a smaller than standard burner throat to enable high exit velocity of secondary air when operating at full load. This ensured that the desired fuelair mixing pattern was still maintained for ame stability and NOx control under deep-staging operating conditions. The twin-uid, I-jet atomizer used is a BWRC design. It has four discharge holes drilled in the spray cap at inclined angles. The use of caps with dierent discharge hole sizes allows for handling various fuel and airow rates to enable atomization air/fuel ratio (A/F) adjustments for both HFO- and CPW-ring tests. The spray angle was generally small compared to the atomizers used in full-scale units because of the single burner conguration and the relative narrowness of the furnace in the SBS-II. For all of the tests, the atomizer was axed in such a way that the endcap was ush with the burner exit. A 60 open-blade swirler was mounted behind the atomizer to introduce swirl to the core air and to stabilize the ame. A high-velocity thermocouple (HVT) probe was used for the measurement of the furnace exit gas temperature (FEGT). Air and ue gas ow rates were measured with calibrated Venturi ow meters, corrected for process temperature and pressure and gas composition (molecular weight). There were gas analyzers for O2, NOx, and CO in the convection pass area and a stack gas analysis system for O2. After ltering and drying, ue gas composition, in particular, CO, O2, and NOx concentrations, was measured and recorded by calibrated analyzers. There was an oxygen concentration in situ analyzer (wet basis) at the convection pass outlet. The measurement principles of the analyzers are as follows: the moisture device was a MAC Instruments MAC 125 analyzer (proprietary solidstate process); the measuring probe of the in situ O2 (wet basis) analyzer was a zirconium oxide sensor; the measuring probe of the in situ O2 (dry basis) analyzer was a paramagnetic device; CO was measured by the non-dispersive infrared (NDIR) technique; a chemiluminescence probe was used for NOx analysis. Particulate sampling was performed on a horizontal duct at the convection pass exit using a BWRC custom-designed and proprietary, high volume sampling probe, where ue gas was extracted through six nozzles along a penetrating tube pseudo-isokinetically. Particulates collected on the lter paper were analyzed later to determine loss on ignition (LOI) or unburned carbon. The ame shape was monitored by means of a FlameView camera. The latter is able to generate two-dimensional temperature maps from the live ame image using the two-color pyrometry principle. A LAND
C

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two-color pyrometer was also used to perform single-point ame temperature measurements at the near burner zone. 2.3.2. Fuel Handling System and Test Procedure. The fuels under scrutiny, rst, No. 6 fuel oil (HFO) and, subsequently, CPW, were transferred to the 300 gallon day tank prior to testing. The tank was restocked during tests as needed. HFO was preheated overnight in the tank using electrical belt heaters. The HFO nal delivery temperature (74 C) was adjusted by heat tapes installed outside the pipes. CPW was stored, pumped, and atomized at room temperature. A Moyno progressive cavity pump delivered both fuels to the atomizer/burner. The fuel delivered to the XCL burner was atomized by plant compressed air metered by calibrated orices using the I-Jet atomizer positioned along the centerline of the burner. Each test began with a 2 h warming period that involved heating the combustion air using a trim heater and heating the entire furnace by ring natural gas through the igniter. Once suitable furnace conditions were reached, liquid fuel was introduced gradually to the burner, atomized, and ignited by the natural gas support ame. The natural gas heat input was gradually reduced and eventually shut o as the desired furnace load was approached. The furnace was then allowed to warm for at least 1 h more until the convection pass exit temperature and gas species concentrations reached steady-state levels before test startup. Computerized data acquisition was used for monitoring and recording furnace-operating conditions, such as the ow rate, temperature, pressure, and species composition at various locations. Flue gas component concentrations, in particular CO, O2, and NOx, were measured continuously at the convection pass exit. Visual observations of the ame were performed and documented for every test and throughout the intermediate adjustment. FEGT and LOI measurements were conducted on selected tests for both HFO and CPW fuels. During the measurement, the HVT probe was placed perpendicular to the ue gas ow to obtain temperature measurements at ve dierent locations. The collected y ash samples were analyzed for unburned carbon using a modied American Society for Testing and Materials (ASTM) D6316 method. It was converted to combustion eciency on a heating value basis during data analysis. Combustion tests were performed at various operating conditions. Test variables were selected to best address the objective via variations of the main and support fuel heat input, burner stoichiometry ratio, burner swirl, atomizer spray angle, and atomizer A/F. Qualitative observation of the ame shape and stability were made during each test. It is worth mentioning that there was no clogging of the atomizer tip while ring CPW.

3. CPW PHYSICAL PROPERTIES 3.1. Particle Size and Stability. The Sauter mean diameter or D(3,2) of dry petcoke before processing was about 15 m, and as mentioned in section 2, the petcoke preslurry would settle almost immediately. The CPW Sauter mean diameter after wet comminution was about 5 m and was very stable to sedimentation. In fact, the sedimentation pattern was very similar to the pattern reported for a colloidal coal in water suspension.3 Within 24 h of preparation, a thin, millimeter-sized layer of clear water would appear at the top; this layer thickness was independent of the container size and was likely due to some condensation of water after manufacturing and storing. During the rst 2 weeks, no changes would be observed and the uid would be homogeneous from top to bottom. Then, during the next 10 weeks, the clear water layer would increase in size, reaching a thickness equivalent to about 5% of the total sample height, while the suspension underneath would become more viscous but without a well-dened (bottom) sedimentation layer. Sample homogenization would be relatively easy by mixing a few minutes with an overhead stirrer. At 6 months after preparation and once the totally clear water layer had reached a stable thickness (about 15% of total
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Energy & Fuels height) in the 55 gallon container, samples of the suspension were taken at the top, middle, and bottom of the drum and the particle size was virtually the same at all levels. Hence, the sedimentation behavior can be described as structure-shrinking, while water diuses to the top or compaction. Notwithstanding, CPW is remarkably more stable than conventional slurries that require additional compounds, such as polymers in solution, to reduce sedimentation. This behavior stems from the microscopic morphology of the uid: it can be viewed as a pseudo-uid consisting of a large colloidal fraction, in which a spectrum of sizes of non-colloidal particles is suspended. Under this perspective, the colloidal pseudo-uid is a stiened phase (strong colloidal interparticle forces) that prevents the settling of larger particles. This concept was rst advanced by Probstein7 and was also discussed in our previous publication.3 3.2. Rheological Behavior and Fuel Handling. As mentioned in section 2, the rheological behavior of the CPW was evaluated using a rotational rheometer set with parallel plates and a gap wide enough to minimize the particle interaction with plate walls (1 mm). Steady-state ow curves were carried out in a wide shear rate range (0.11000 s1) and at 25, 35, and 45 C. Apparent viscosity as a function of the shear rate and temperature is plotted in Figure 1, and as shown,

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beyond 1000 s1, it can be conjectured that the ow curves may intersect at higher shear rates and the usual behavior of viscosity versus temperature may be reached. On the other hand, it is also possible that the curve convergence is due to a slip at the wall, a phenomenon previously observed in a colloidal coal-in-water suspension.3 The slip at the wall is produced by migration of the continuous uid to the wall of the moving disk, forming a so-called lubricated layer. The formation of this layer marks the onset of slip that is predominantly a hydrodynamic phenomenon. During the combustion tests, a viscosity index of the fuel was monitored at room temperature using a Brookeld viscometer rotating at 100 rpm. This type of viscometer is not a rheometer because the stress eld is not known as a result of the high complexity of the ow; in consequence, the viscosity reading can only be used as a relative ranking of ow characteristics.10 The viscosity index during the tests would vary from 1400 to 1800 cP, 10 s after rotation onset. The fuel was discharged into the day tank and was recirculated before every combustion test. Further, the material was pumped and atomized without any diculty, such as plugging by sedimentation buildup.

Figure 1. Apparent viscosity as a function of the shear rate and temperature of CPW. Measurement using a rotational rheometer and parallel plates.

viscosity increases with temperature. The material is also increasingly shear-thinning with the temperature, and the curves tend to converge at high shear. Plotting shear stress as a function of the shear rate allowed for a clear reading of yield stress, which was virtually 0 Pa at 25 C, 60 Pa at 35 C, and 350 Pa at 45 C. These results point to complex particle interactions at the molecular and microscopic level; this phenomenon have been observed before in coal-in-water slurries.8,9 One plausible explanation of the observed behavior is as follows. It is wellknown that non-ionic surfactants, such as the surfactants used to prepare the slurry, become less hydrophilic as temperature increases. This eect makes the petcoke particles more hydrophobic as temperature increases, thereby inducing a stronger attraction between the particles. This promotes the formation of a stier microstructure that, nonetheless, crumbles at high shear. In fact, this eect is reversible in the sense that a sample experiencing heating and cooling cycles recovers its former lower viscosity when cooled. The macroscopic eect of structuring is observed at the lowest shear rates; yield stress and viscosity augment about 10fold each 10 C change of temperature increase. As the shear rate is increased, the microstructure is gradually destroyed and viscosity is rapidly reduced. Although we could not measure
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4. COMBUSTION PERFORMANCE 4.1. Baseline HFO Tests. Baseline characterization tests were carried out by ring No. 6 HFO to obtain reference data for comparison to the CPW fuel. When burner spin vane angles, core air ow, and optimum burner settings were adjusted, attached stable ames were achieved at full load with nominal 3% (v/v) excess oxygen in the convection pass. The eects of burner stoichiometry and fuel heat input variations were examined in subsequent tests. A y ash sample was taken at the optimum condition, with the burner stoichiometry ratio close to unity. Because of the low ash content of the HFO, it was dicult to collect y ash samples for every test. FEGT measurements were performed for every test to characterize furnace side heat transfer. Selected data are presented in later sections in comparison to CPW test results. 4.2. CPW Tests. Performance and emission characteristics of CPW combustion were evaluated systematically via parametric testing. Generally speaking, a low-volatile and high water content fuel is dicult to ignite, maintain a stable ame, and burn out completely. However, in this case, it was relatively easy to achieve good combustion performance, using the existing burner and atomizers. The startup and shutdown procedures for both CPW and HFO ring were similar. In the case of CPW, the fuel temperature was not a concern during startup because CPW was red at room temperature and no heating was required. Firing liquid fuels, including CWS, in commercial boilers starts by injecting the fuel into the hot furnace in the form of a ne spray to increase its surface area and promote fast heating of the fuel droplets, quickly releasing any moisture and volatile matter associated with the fuel. The latter reaches ignition at some point, further heating and igniting the remaining fuel residue (char) until complete burnout, provided that it remains long enough inside the hot furnace, before reaching the furnace exit. Steam-assisted atomization using internal mix atomizers is the preferred method for generating a ne spray in commercial HFO boilers. It also became the norm in CWS ring. Air is a valid alternative and is the uid assisting atomization in this work.
dx.doi.org/10.1021/ef301249q | Energy Fuels XXXX, XXX, XXXXXX

Energy & Fuels There are other forces at work in CWS or CPW that oppose the breaking of the liquid into a ne spray, not encountered in HFO atomization. These are complex particleparticle and particleliquid interactions, which are further aected by the presence of a surfactant. In addition, CWS rheological behavior seems to be more important than viscosity during air- or steamassisted atomization.11 CWS prepared from a ne grind requires a larger steam/CWS mass ratio to produce the same droplet size than CWS from a coarser grind.11 Highly concentrated CWS also gives coarser sprays than less concentrated CWS, keeping all other conditions the same. Steam or air at sonic velocities at the atomizer tip outlet ports is desirable for the best CWS atomization results.11 A CWS or CPW droplet, suddenly subjected to fast heating inside the boiler furnace, goes through the above-mentioned sequence: (i) moisture evaporation, (ii) devolatilization, accompanied by swelling and particle agglomeration in some caking coals (not the case for petcoke), (iii) volatile combustion, and (iv) char combustion. Step i is longer for CWS and CPW (because of moisture evaporation) than for the parent dry pulverized petcoke, therefore delaying step ii, and both steps overlap. This eect extends the parent fuel heating time to get to step iii. CPW droplets, once subjected to the hot furnace environment, reach the water boiling point quickly, remaining at this temperature until all of the liquid water is consumed. The water evaporation time is directly proportional to the droplet diameter squared. Besides being subjected to high heat transfer by radiation, convection-enhanced evaporation from the hot gas strong recirculation toward the ame root also helps to increase the water evaporation time and, consequently, the ame stability. It follows that it is reasonable to expect that high air swirl should benet ame stability during CPW ring. Coal particle agglomeration leads to larger, longer burning chars, and this is responsible for high levels of unburnt carbon in ash when ring coal in HFO-designed boilers. This is much less of a problem for the non-caking petcoke particles. Therefore, ne grinding, as in CPW, must help to reduce char size and burning time. Colloidal petcoke particles take char size and burning time to lower values beyond the values found in conventional CWS or pulverized coal. These two factors contribute to ame stability and low levels of unburnt carbon, within the in-furnace residence time of about 1 s, for HFOdesigned boilers. Another factor that helps CPW and to a less extent CWS to reduce the unburnt carbon values is through the reaction between steam and char, as shown in eq 1.
C(s) + H 2O(g) CO(g) + H 2(g)
(1)

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the CPW rst-ignition attempt. The gas load was gradually reduced accompanied by the gradual increase of the CPW ow rate. During this process, burner vane adjustment was performed to keep the ame attached and stable. The burner settings were 20 and 60 open for inner and outer vanes, respectively. The CPW ame stayed stable and attached when the natural gas fuel was cut o completely, which happened at the very rst CPW ring test without requiring any process variable adjustment. The following patterns were observed during the rst test with CPW ring at full load (6200 MJ/h). CPW produced a relatively translucent ame compared to a typical coal and HFO counterpart. The radiation emission in the visible spectral region was weak, although no quantitative measurements were conducted. This unique ame appearance was unexpected for petcoke. It seems to be a distinct feature of this new fuel (see Figure 2).

Figure 2. Photograph of the CPW ame at 5900 MJ/h, BSR of 0.85, and A/F ratio of 0.19.

This reaction is more relevant for the water-based slurries than for pulverized coal combustion,12 and it becomes important above 1000 C, which is a value well within typical furnace temperatures. It takes place simultaneously with other reactions, such as C(s) + O2(g) CO2(g)
C(s) + CO2(g) 2CO(g)
(2) (3)

A detailed account of the parametric testing results is presented next. 4.3. Support Fuel Minimization at Full Load. A conservative approach was favored for this activity. A ow rate equivalent to 3200 MJ/h of natural gas was used to assist
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A minimal amount of sparkles was observed at the nearburner zone for this test (and most other tests). No sparkles were observed at the horizontal furnace section, leading to the convection pass. In the absence of a quantitative evaluation, this observation presents evidence on the ease of atomization and rapid combustion of the CPW fuel. This is most likely related to the colloidal-sized particles present in the fuel. The CPW ame temperature showed a slight increase with the distance from burner throat. The temperature moved to 1336 C at 180 cm from 1312 C at 20 cm from the burner. However, it was still lower than the HFO temperature (1565 C on average) because of the high water content. In contrast, FEGT measurements indicated that CPW combustion exhibited heat absorption at the furnace section similar to HFO combustion. At the outlet of the convection pass, ue gas temperatures were also similar between CPWand HFO-ring cases, as shown in Figure 3. This gure depicts FEGT as a function of the distance to the furnace wall for the same burner stoichiometry ratio (BSR) value (0.85). As expected, both curves for CPW and HFO tend to decrease as the furnace wall is approached. The observed behavior is an indication that convection pass heat absorption characteristics were similar under the two ring modes. Further, this is also an indication that the increased surface area of CPW is helping to improve combustion characteristics. The same patterns were observed for 75% of full load. At 50% load (3150 MJ/h), the ame became unstable.
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Figure 3. FEGT as a function of the distance to the furnace wall for a BSR value of 0.85.

4.4. Burner Optimization Tests. Parametric tests were carried out to assess the impact of burner vane settings on ame stability and emissions with 100% CPW fuel without any natural gas support. In general, the inner vane adjustment had greater eects on enhancing ame stability than the outer vanes because of the more intense swirl generated near the fuel injection point. However, excessive swirl, especially on the outer ame zones, could cause the ame to are and ame length to shorten undesirably. Figure 4 shows comparisons of (a) CO and (b) NOx emissions of CPW combustion with ve dierent burner vane

introduced by the burner. Overall, 20 60 setting produced the best ame attachment and length and was used for all subsequent tests. In comparison to the optimal burner vane setting for HFO (30 75 open), more swirl was needed to stabilize the CPW ame. However, stable CPW combustion was achieved on the same burner with no hardware modications. Further, burner vane settings had little impact on CO emissions (Figure 4), while NOx emissions did vary. 4.5. Atomizer A/F Optimization Tests. CPW atomization using steam is commercially more acceptable, but given the low fuel temperature and high fuel water content, air was used as the atomization medium. Air was also used for HFO atomization for comparison purposes. From a commercial application point of view, there is an interest in reducing atomization gas usage and, therefore, lowering plant operational cost. We conducted tests to compare combustion and emission performances to various atomizer A/F ratios and two atomizers. Figure 5 recaps the combustion eciencies and major emission data at various A/F ratios for CPW. Two

Figure 4. CPW combustion emissions at various burner vane settings. (a) CO emissions in ppm by volume of dry gas and (b) NOx emissions in ppm by volume of dry gas. Tests conditions: 6300 MJ/h, BSR range of 0.920.95, and nominal 3% (v/v) excess O2 at the convection pass.

Figure 5. CPW combustion and emission performances at various atomizer mass A/F ratios. Tests conditions: 6300 MJ/h, BSR range of 0.920.95, and nominal 3% (v/v) excess O2 at the convection pass. Conguration 1, 0.175 design A/F ratio; conguration 2, 0.25 design A/F ratio. Atomizing angle at 50.

settings. The next paragraph gives an outline of the observations and measured data. Flames were detached from the burner throat when the inner vanes were set at a 30 opening (rst two conditions in Figure 4). Flame attachment and stability were signicantly improved when the inner vanes were set at a 20 opening (last three conditions in Figure 4), although with the outer vanes set to 65 or more, the ame was detached. With 20 50 opening settings, the ame was ared because of excessive swirl
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congurations of discharge hole sizes (conguration 1, 0.175 design A/F; conguration 2, 0.25 design A/F) and similar 50 spray angle were used to vary A/F ratios. Combustion eciencies were not greatly aected by the variations in the atomizer A/F ratio, although ames were slightly detached at the lower ends of the A/F ratio range for both atomizer congurations. Atomization performance might be less than ideal in these cases, but particle burnout was still excellent probably because of the increased surface area associated with the colloidal-sized particles. This indicates that the particles in a single droplet did not burn as an agglomerate during devolatilization and char burnout. It is
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Energy & Fuels worth pointing out that CPW combustion eciencies were slightly better with natural gas support than without, although the dierences were within the measurement uncertainty. CO emissions remained in the range between 30 and 40 ppm by volume of dry ue gas. Their independence to the atomizer A/F ratio is probably due to the reasons mentioned above. Even though higher atomization air ow for a given atomizer design produces more ne droplets that are faster to evaporate and combust, no clear trend was observed for NOx emissions with the atomizer A/F ratio. This indicates that atomization adjustment played a secondary role to burner stoichiometry ratio adjustments, in terms of NOx control. However, NOx formation tends to increase when the ame starts to detach, probably because of the less eective control of air/fuel mixing at the near burner zone, in line with Curtis ndings.13

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5. RESULTS AND DISCUSSION The calculated boiler eciency losses were 17.2 and 13.5% for the CPW and HFO cases, respectively (or 3.7 percentage loss with respect to HFO). Relative to the HFO-ring data, the greater boiler eciency loss for CPW ring was primarily due to the high moisture content in the ue gas leaving the boiler, which is related to the water present in the CPW fuel. However, there is a certain boiler eciency gain associated with the increased ue gas mass and velocity, inherent to CPW ring compared to HFO, at the same heat input, which increases to some extent the convection heat transfer to the tube banks of the boiler. The measured boiler eciency is the net result of these two counteracting eects. The CPW high combustion eciency and outstanding handling characteristics allows for the consideration of CPW as a practical fuel with commercial applications. This opens up the possibility of using petcoke in commercial boilers designed to re HFO, without any additional fuel support, even at reduced thermal inputs (75%). The magnitude of the CPW outstanding combustion performance is better grasped and quantied by the data depicted in Figure 6. The graph shows actual combustion eciencies [for dry and ash-free (daf) coal] presented by Juniper and Pohl,14 displaying data obtained from ring coal, for a wide range of volatile matter content, including full-size boilers and combustion pilot plants from Australia and the U.S.A.

It should be noted (Figure 6) that there is no data for fullsize boilers using coal having a volatile matter content below 25%. It is also shown how fast carbon burnout (in pilot plants) deteriorates as the coal volatile matter decreases below 25%. This is the result of the diculties associated with maintaining a stable ame, using coal of volatile content below this level. Carbon burnout values (at 3% excess O2) from the CPW combustion tests at BWRC were included in the graph (), showing a completely dierent behavior from previous experience, pointing to the fact that colloidal petcoke in water suspensions should be considered a new category of fuel showing outstanding combustion properties. This improved CPW carbon burnout values are the result of the much higher petcoke colloidal particle count and, consequently, higher particle surface area in CPW, which translates into an enhanced particle reactivity. These particles are the particles responsible for the much improved ame stability, which likewise directly leads to elevate the CPW carbon burnout values, as compared to conventionally pulverized petcoke or coal particles of similar or even higher volatile matter content.

6. CONCLUDING REMARKS In this work, we have advanced results concerning the combustion behavior of a new material. The technology presented here essentially maps solids fuels, such as petcoke and coal, into a gas from the combustion standpoint. This is achieved by taking the specic surface area available for combustion to values typical of the colloidal domain without paying a great energy expense. Further, it should be said that the mapping in question must be made in the presence of water to prevent the colloidal particles from becoming airborne. The resulting material is a liquid that ows appropriately at room temperature and is thus amenable for power generation in boilers and low-speed diesel engines at expenses that are fractions of currently used fuels, such a HFOs.

AUTHOR INFORMATION

Corresponding Author Notes

*E-mail: briceno@nanodt.com. The authors declare no competing nancial interest.

ACKNOWLEDGMENTS We are grateful to DTE Energy for supplying the petroleum coke for this test. We also acknowledge the support of NDTs personnel in manufacturing the samples. DEDICATION To our knowledge, this is the last contribution advanced by Daniel D. Joseph before his passing on May, 2011. We dedicate this work to his memory. ABBREVIATIONS A/F = air/fuel ratio BSF = boiler simulation furnace BSR = burner stoichiometry ratio BWRC = Babcock and Wilcox Research Center COS = coaloil slurry CWS = coalwater slurry CPW = colloidal petroleum coke in water suspension daf = dry and ash free FEGT = furnace exit gas temperature
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Figure 6. Coal burnout results as a function of the volatile content (daf) from full-size boilers and combustion pilot-scale plants. (, , and ) Data as presented by Juniper and Pohl14. () Comparison to petcoke burnout and from this work at 3% excess O2.
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Energy & Fuels HFO = heavy fuel oil HVT = high-velocity thermocouple LOI = loss on ignition

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REFERENCES

(1) Khodakov, G. S. Coalwater suspensions in power engineering. Therm. Eng. 2007, 54 (1), 3647. (2) Wibberley, L.; Palfreyman, D.; Scaife, P. Ecient Use of Coal Water Fuels; CSIRO Energy Technology, Australian Governments Cooperative Research Centres Program: Pullenvale, Queensland, Australia, 2008; Report 74. (3) Nunez, G. A.; Briceno, M. I.; Gomez, C.; Joseph, D. D.; Asa, T. Colloidal coal in water suspensions. Energy Environ. Sci. 2010, 3, 629 640. (4) Huang, X.; Jiang, X.; Han, X.; Wang, H. Combustion characteristics of fine and micro-pulverized coal in the mixture O2/ CO2. Energy Fuels 2008, 22, 37563762. (5) Cheng, J.; Zhou, J.; Li, Y.; Liu, J.; Cen, K. Effects of pore fractal structures of ultrafine coal water slurries on rheological behaviors and combustion dynamics. Fuel 2008, 87, 26202627. (6) Yu, D.; Xu, M.; Sui, J.; Liu, X.; Yu, Y.; Cao, Q. Effect of coal particle size on the proximate composition and combustion properties. Thermochim. Acta 2005, 439, 103109. (7) Probstein, R. F. Physicochemical Thermodynamics, 2nd ed.; Wiley Interscience: New York, 1994; Chapter 9, p 298. (8) Roh, N. S.; Shin, D. H.; Kim, D. C.; Kim, J. D. Rheological behavior of coalwater mixtures. Fuel 1995, 74 (9), 13131318. (9) Tsai, S. C.; Knell, E. W. Viscometry and rheology of coal water slurry. Fuel 1986, 65 (4), 566571. (10) Macosko, C. Rheology, Principles, Measurements and Applications; VCH Publishers: New York, 1994; Chapter 5, p 223. (11) Thambimuthu, K. V.; Whaley, H. In Principles of Combustion Engineering for Boilers; Lawn, C. J.. Ed.; Academic Press: New York, 1987; Chapter: The Combustion of CoalLiquid Mixtures, pp 391 392. (12) Hathl, V.; Ramezan, M.; Winslow, J. Industrial and Utility-Scale CoalWater Fuel Demonstration Projects; Pittsburgh Energy Technology Center, U.S. Department of Energy: Pittsburgh, PA, Jan 1993; Technical Report 93/4. (13) Curtis, J. S. Coal Particle Flow Patterns for O2 Enriched, Low NOx Burners; Purdue University: West Lafayette, IN, Sept 2004; Final Report for the Department of Energy. (14) Juniper, L. A.; Pohl, J. H. Design of pilot scale rigs to simulate combustion processes. Proceedings of the Australian Symposium on Combustion; Gawler, South Australia, Nov 1995.

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