APPLIED CATALYSIS AGEL Copy ELSEVIER ‘Applied Catalysis A: General 210 (2001) 137-150 wortelseviercomMocateapeaia Attrition resistance of cobalt F-T catalysts for slurry bubble column reactor use Dongguang Wei*!, James G. Goodwin Jr.**, Rachid Oukaci®, Alan H. Singleton? * Deparament of Chemical and Petroleum Engineering, University of Pisburgh, Pittsburgh, PA 15261, USA ® Energy ncerational Corporation, 135 Wiliam Piz Way, Pittsburgh, PA 15238, USA ~ [Received 23 March 2000; received in revised form 1 September 2000; accepted 8 September 2000 Abstract, ‘There exists much current interest in the use of supported Co catalysts and slurry bubble column reactors (SBCR) for the conversion of natural gas to higher bydrocarbons via the Fischer-Tropsch (FT) synthesis. Catalyst attrition resistance is extremely important in the operation of slurry-phase reactor systems because of potential problems with plugging of system filters and/or contamination of the liquid products. This paper addresses the effects of different supports, promoters, and ‘preparation methods on the attrition resistance of Co FT catalysis for SBCR use. ‘The calcined supports had attrition resistances (inversely related to % fines <1 um generated during attrition testing) as follows: =Alg03 > TiOp(tutile) >> SiOz Loading of Co onto the supports improved the attrition resistances of both alumina and silica significantly. It has essentially no effect on titania, The resulting catalysts had attrition resistances in the ordex Co/Al03 > Co/SiOz > Co/TiOz(euile) >>> Co/TiO. (anatase) ‘The addition of small amounts of metal (Ru, Cu) and oxide (La, Zr, K, Cx) promoters had mainly small effects on the attrition resistance of the supported Co catalysts. However, it would appear that the addition of Zr to Co/alumina had a negative Impact on its attrition resistance. The different preparation methods used in this study (aqueous impregnation, non-aqueous impregnation, and kneading) did not appear to have a significant effect on catalyst attrition resistance. © 2001 Elsevier Science. BV. All rights reserved. Keywords: Co catalysts; Slurry bubble column reactor; Fischer-Tropsch synthesis; Atrtion resistance; Alumina suppor; Titania suppor; Silica support 1. Introduction Cobalt catalysts are known to be very effective for the Fischer—Tropsch (F-T) synthesis [1-3]. With the * Conrespording author : ‘i oe cae: poste Gageay cluesl Gel Goodyta Ie, addition of some metal (ruthenium, rhenium, or other "Present adress: Insite of Coal Chemistry, Chinese Academy noble metals) and oxide (zirconia, lanthana, chromia, of Sciences, Taiyuan 030001, PR China etc.) promoters, the activity and selectivity can be (0926-860XI01S ~ see from matter © 2001 Elsevier Science B.V. All rights reserved, PIL: $0926-860%(00)00792.4138 D. Wei et al /Applied Catalysis A: General 210 (2001) 137-150 adjusted in a wide range. Various refractory supports have also been used to prepare Co FT catalysts. Alu- mina (4-9), silica [10-15], and titania [16-21] sup- ports have been the most widely studied and patented during the past two decades. The most frequently used preparation methods reported in the literature involve some form of impregnation using either aque- us or organic solutions [22]. In order to achieve high metal dispersion, metal-support interactions, and/or ‘metal promotion, various procedures have been ap- plied, including multi-step impregnation, molten salt impregnation, a combination of impregnation and kneading, as well as different pretreatments (22). F-T synthesis involves a group of highly exothermic reactions. Much recent work has been concentrated on the’ use of slury-phase reactors, such as slury ‘bubble column reactors (SBCRs), due especially to their high heat removal capabilities. Recent research [23-25] has shown that noticeable catalyst size reduc- tion does result from extended SBCR and CSTR runs, indicating clearly the existence of catalyst attrition in slurry-phase reactors. Attrition increases the number of catalyst particles and reduces the average particle size, The attrited catalyst is very difficult to separate from liquid products since the catalyst does not set- le well, and more seriously, the fines entrained by liquid flow can result in plugging of effluent stream filters. This diminishes reactor performance. There- fore, slurry-phase processes are extremely demanding ‘on a catalyst from the viewpoint of physical strength. Many catalysts that could be very promising, based solely on their activity and selectivity, fail to have practical application because of the rate of attrition experienced in the abrasive environment. ‘The phenomenon of catalyst attrition has long been recognized and studied for fluidized bed processes [26-29]. Much emphasis in the published research hhas centered on the influence of operational variables, ‘modeling of the attrition process, etc. [26-29]. The influence of the nature of the catalyst materials and the effect of catalyst preparation methods on attrition resistance have seldom been studied. However, the nature of the catalyst material and the preparation ‘methods used can play significant roles in determining catalyst attrition resistance [30-32]. ‘Various types of measurement methods have been developed for evaluation of catalyst strength or atti- tion resistance, such as compression, rotating drum, fluidized bed, jet-cup, and ultrasonic tests [23]. Each of these methods, while having much in common as a ‘group, has unique features with regards to character- izing the strength of a catalyst. However, all may be suitable under certain operational conditions to pre- dict catalyst attrition in specific reactors. For instance, the ultrasonic test, which causes catalyst attrition primarily through cavitation in catalyst suspension, hhas recently been found under proper measurement conditions to be able to predict catalyst attrition in SBCRs (23). In this paper, the results of an investigation of the attrition resistance of supported cobalt F-T catalysts are reported. Two series of catalysts were studied. (One series was run in a laboratory-scale SBCR under F-T conditions for 10 days. The other series was studied using an ultrasonic attrition testing procedure. ‘The effects of different supports, compositions, and reparations on attrition resistance were determined and are discussed. 2, Experimental 2.1. Materials 2.1.1. Supports ‘y-AlOs: Catapal-B alumina from Condea/Vista in the boehmite form was calcined at 500°C for 10h to ‘convert it to y-alumina. SiOz: Davison Grade 952 sil- ica was calcined at 500°C for 10h. TiOp: Degussa P25 titania was used to prepare the catalyst support. Two types of TiO2 were prepared. Rutile type: the titania was wetted to incipient wetness with distilled water, then dried in an oven at 60°C with moderate stiring. It was then calcined at 650°C for 16h resulting in a support having ca. 97% rutile. Anatase type: the pro- cedure was the same as in rutile preparation except for the calcination temperature (350°C). The resulting ‘material was mainly in the anatase form. Al supports were pre-sieved to the desired particle size range (usually greater than 38 jm) before catalyst preparation. XRD pattems of some of the supports are shown in Fig. 1. 2.1.2. Cobalt and promoter compounds Co, Ru, La, K, Cu, Cr, and Zr were from cobalt nitrate [Co(NO3)2-6H,0], ruthenium nitrosyl nitrate,D. Wei et al /Applied Catalysis A: General 210 (2001) 137-150 139 1000 800 2 600 7 Cold s 400 Tio, 200 Coat SiO, Cos ° ALO, 2 40 6 80 2Theta (degree) Fig. 1. XRD paters of AlzO3, Si02, TiO (rutile, Co-8 (CoV/Al,05), Co! (Co/Si0,), and Co-14 (Co/Ti02). lanthanum nitrate hexahydrate, potassium. nitrate, ‘copper nitrate [Cu(NO3)2-xH,0], chromium ni- trate [Cr(NO3)3-9H20}, and zirconium oxonitrate [Z:O(NOs)2}, respectively. All chemicals used were of high purity (CP). 2.2. Catalyst preparation ‘The identity and characteristics of the supports used ‘are given in Table 1. All 16 catalysts used in this study were prepared by impregnation, kneading, or their combination. All catalysts were also sieved to the desired particle size range after the final calcina- tion step. The composition, physical properties, and brief description of the preparation methods of the 16 catalysts are summarized in Tables 2 and 3. Specific methods used were as follows: 2.2.1. Aqueous incipient wetness impregnation ‘Most of catalysts [Co-1 > Co-4, Co-6 + Co-8, Co-9 (Ist step), Co-10, Co-L1, Co-13 (2nd step), and Co-15] were prepared with this method. The support was impregnated with an aqueous solution contain- ing selected metal salts using an appropriate quantity Teble 1 Sources, preteatments, and properties of supports used Suppor ‘Source Preveaiment BET surface Bulk density area (m"/g) (wicc) rAhOs Commercial, spray dried Caleined at S00°C for 10h 206 0.68 Caapal-B alumina SiO Commercial, spray died —Caleined at SOO*C for 10h 219 027 Davison (Grade 982) silica TiO; (R) 97% rule 3% anatase Commercial Degussa ‘Werted with wate, thea 2 126 2S sitania ‘calcined at 650°C for 16h ‘TiO, (A) mainly anatase (Commercial Degussa Wetted with wate, then - - P25 tania calcined at 350°C for 16h0 D. Wel etal /Applied Caalyss A: General 210 (2001) 137-150 Twe2 | ‘Summary of composition and preparation methods of supported cobalt F-T catalysts (Co-1 —> Co-7) used for slarry bubble column reactor saies Caalyst Conposion Brief desciption of preparation method oor 1B wt% Co/AlaOs Single step aqueous incipient wetness impregnation with cobalt nae souton co 20% Co, 0.43% Ru, 1.0% LazO3/AlO3 ‘Wo step aqueous incipient weess impregnation: (1) Co, then calcined, followed by (2) Ru and La C03 20% Co, 0.5% Ru, 03% K/ALOs Single step aqueous incipient werness impregnation ‘with Co nitrate, Rants nivate and K nitrate solution co 208Co, 5% Co, 4% CUALOs Two sep aqueous incipient wetness impregnation: (1) Cu and Cr, then ealeined?,folomed by (2) Co cos 20% ColsiO: Single step kneading with aqueous solution 110% of pore volume cos 20% Co, 8.5% ZSiO2 “Two step aqueous incipient wetness impregnation: (1) Ze, then caleined, followed by (2) Co co7 20% Co, 8.5% Zr, 0.5% Ru, 03% K/SIO2 ‘Two step aqueous incipient wetness impregnation: (1) Ze, then calcined, followed by (2) Co, Ru and K * Calcined in air at 300°C for Zh (beating rate of ca. 1°CY/inin to 300°O). Calcined in air at 750°C for 24h (heating rte of ea. 1°Clmin to 750°C). to give incipient wetness with the desired loading of 2.2.2, Aqueous kneading ‘metal or oxide. The catalyst precursor was then dried Some of the catalysts (Co-5, Co-12, and Co-13 in air at 120°C for 12h and calcined in air at 300°C (Ist step)] were prepared by this method. A mixture for 2h (heating rate of ca. 1°C/min to 300°C). ‘comprised of the support and an aqueous solution of ‘Tbe 3 Preparation methods, compositions, and physical properties of supported cobalt FT catalysts (Co-8 > Co-16) used for ation testing ‘Catalyst Composition BET surface Bulk density Brief description of preparation method sea (ng) (emi) CoS 20% CAL; 3 091 Single step aqueous incipient wetness impregnation with cobalt nivate sluion C9 20% Co, 043% RY 14D 107 ‘Two step impregnation: (1) aqueous incipient wetness 1.0% La,03/Al 0) with Co, then calcined, followed by (2) impregnation of acecone/thanol solution of Ru and La CoO 20% Co, 8.5% ZALOs 185 os Single step aqueous incipient. wetness impregnation with Co nitrate and Zr oxonitate solution Coll 20% ColSiOn au oat Single step aqueos inspient wetness impregnation with cobalt nitrate solution Co12 20% Co, 8.5% ZWSIO, 207 04s Single sep aqueous kneading with 110% SiO; pore ‘yolume solution of Co + Zr for 3.5 hours COIs 20% Co, 85% 2S, 209 047 “Two steps (1) aqueous kneading (110%) with Co so- tion, then caleined®, followed by 2) aqueous incipient ‘wetness impregnation with Zr solution Cold 20% Co/TIO2 (R)E u 135 ‘Single step acetone impregnation Cols 12% CoO (Ayt 38 086 Two np agents impregnation: (1) 60% of Co loudng, thea calcined’, followed by (2) the remaining 40% Co Col6 12% Corin RF 6 135 Single tp scone impregnation * Calcined in air at 300°C for Zh (heating rate of 1°Cimin to 300°C) Calcined in air at 250°C for 3h (heating rate of 1°Ciin to 250°C). Contained 979 rutile and 3% anatase. Mainly anatase.D, Wet etal /Applied Catalysis A: General 210 (2001) 137-150 oo selected metal salts (Where the aqueous solution was 110% of the pore volume of the silica) was kneaded for 3.5h. The catalyst precursor was then dried in air for Sh at 120°C with moderate stirring and calcined in air at 300°C for 2h (heating rate of ca. 1°C/min to 300°C). 2.2.3. Organic impregnation Some of the catalysts [Co-9 (2nd step), Co-14, and Co-16] were prepared via impregnation with organic solvents. For Co-14 and Co-16, the titania support was impregnated with an acetone solution of cobalt nitrate. Approximately I ml of acetone solution of the salts per gram of titania support was used. The catalyst precursor was dried in a rotor evaporator at 25°C and then in vacuum at 140°C for 16h. It was calcined in air at 250°C for 3h, For Co-9 (2nd step), the impreg- nation was carried out with an acetone/ethanol (2:1) solution of lanthanum nitrate hexahydrate and ruthe- nium acetylacetonate. The amount of solution was ca. 2mllg. The excess solvent was removed at 0.01 atm and 25-30°C in a rotary evaporator. The catalyst precursor was dried at 90°C with moderate stirring, 2.3. Catalyst reduction ‘The catalysts used in the SBCR studies (Co-1 —> Co-7) were reduced in a fluidized bed system in @ pure hydrogen flow of 3000ml/g/h by heating at 1°C/min to the required temperature (350°C for alumina-supported, 250°C for silica-supported cat- alysts) and holding for 10h. After reduction, the ccatalyst was transferred in an inert gas to the slurry bubble column reactor for reaction. The catalysts used for the attrition smudies (Co-8 > Co-16) were studied in the calcined state. Co reduction in supported Co catalysts does not appear to significantly affect the attrition properties. 2.4. F-T activity and selectivity ‘The catalysts (Co-l + Co-7) were evaluated in terms of their activity and selectivity in a 1 slurry bubble reactor. Approximately 15 g catalyst and 200g of liquid medium were used in a run. Typically, the reaction was carried out at 220-240°C, a total pressure of 32bar, a Ha/CO ratio of 2, and with 60% Np diluent which helped to dissipate excessive heat generated by the F-T reaction and maintain isother- mal conditions in the slurry bubble reactor. Analysis of the gaseous reactor effiuent (CO, CO2, and C,-Cs) ‘was performed hourly. Liquid products were collected for each 24h period, blended, and submitted for anal- ysis by gas chromatography. Anderson-Shulz-Flory (A-S-F) plots of the liquid product distributions were used to determine the ASF chain growth prob- ability, a. All reaction runs were carried out for 10 days. After reaction, the catalysts were recovered by extraction with toluene reffux for particle size analysis. 2.5. Attrition testing Catalyst attrition was determined by employing an ultrasonic system. The ultrasonic system consisted of a 20kHiz Tekmar TMS01 Sonic Disrupter equipped ‘with a0.5 in, tip, a container, and a hom support frame. ‘The details of this system have been described else- where [23]. A pre-weighed calcined catalyst sample was dispersed in distilled water by light stirring. Sus- pensions were prepared with about 2.5% of solids in a total of 200 mil of distilled water. All catalyst suspen- sions in this work were treated at a 70% energy input of the Sonic Disrupter for 20min. A water bath was used to keep the temperature relatively constant. After ultrasonic attrition testing, the slurry was sampled for particle size distribution analysis. The remainder of the slumy was filtered and dried at 110°C in an oven prior to SEM analysis 2.6. Particle size distribution Particle size distribution measurements were per- formed by means of a Leeds & Northrup Microtrak Particle Size Analyzer (M) which employs a laser beam to determine the particle sizes. The suspension (after ultrasonic attrition testing) was poured into the analyzer sample chamber and then pumped through the Microtrak system, with data being collected in 20 channels of pre-calibrated particle size ranges. ‘The system was controlled with a computer system, and the output from the computer provided a plot of volume percentage versus particle size interval. Al samples were measured before and after attrition measurement.142 D. Wei etal. /Applied Catalysis A: General 210 (2001) 137-150 2.7. Physical characterization ‘SEM: Particle morphology information was ob- tained by using a Philips XL40 scanning electron microscope at an accelerating voltage of 15.0KV in the BSE mode. XRD: X-ray diffraction measurements were per- formed on the calcined samples employing a Philips PW3710 (Cu Ka) powder diffractometer. The XRD patterns were recorded for 26 from 20 to 80° with a 0.04° 28 spacing and 0.5 s exposure time. BET: Specific surface areas of the calcined samples ‘were determined by using a Micromeritics ASAP 2010 instrument and N3 physisorption, 3. Results and discussion 3.1, Reaction and catalyst attrition in the SBCR Catalysts Co-1 -+ Co-4 (supported on Al2O3) and Co-5 > Co-7 (supported on SiOz) were rin in the SBCR. Titania-supported Co catalysts did not have sufficient activities to justify SBCR runs. The reac- tion results, as well as catalyst original volume mean, particle size (VMPS) and the percent decrease in the ‘VMPS during SBCR operation are summarized in Table 4. The activities of AljO3-supported catalysts were generally higher than those supported on SiOz except for Co-4 where AlO3 was modified with Co-Cr. The selectivities of the catalysts (Co-l > Co-7), as defined by the ASF chain growth proba- bility, «, and the methane formation were somewhat dependent on the nature of the promoter used rather than the support type. Since it is not the emphasis of this paper, the catalysts reaction properties will not be discussed further other than to say that the activities and selectivities are within the range of typical Co FT - catalysts proposed for use commercially in SBCRs. Based on the percent decreases in the volume mean particle size of the catalysts (Table 4), it is evident that the catalysts underwent attrition during the 10-day runs in the SBCR. The AlzO3-supported catalysts are all mote attrition resistant than the SiOz-supported ones. Even among the AlaO3-supported catalysts the percentage of size reduction varied greatly. 3.2. Comparison of different supports AlnOs, SiOz, and TiO have been widely used as cobalt F-T catalyst supports. The strengths of the supports themselves contribute significantly to the ultimate attrition resistance of the Co catalysts. Using an ultrasonic system, the attrition resistances of these three supports were measured using water asthe liquid medium. The particle size distributions of the supports ‘were measured before and after ultrasonic testing. The results were plotted in Fig. 2. Volume mean particle size (VMPS) and percent fines produced were chosen as parameters describing particle attrition, since the change in VMPS reflects the particle size reduction in general, while % fines produced is a critical parame ter for slurry-phase reactor applications. The results of the change in VMPS and the % fines produced are ‘Table 4 ‘Summary of reaction results and particle size changes for cobalt F-T catalysts run in an SBCR Caalyst — Composion ‘Activity Selectivity Volume mean particle Decrease in _ GHCIgCaL) Sy ogy ae «Stet (VMPS) (nm) VMBS® (6) Gol 13% GyAnO 1.07 109 08s «a6 84 Co2 20% Co, 043% Ru, 1.0% LeOxAhOs 131 - ogi 677 43 Co3 20% Co, 05% Ru, 0.3% K/AO; 12 73 086728 16 Cod 20% Co, 5% Cu, 4% Co/Al2Os 023 9 os 795 43 CoS 20% ColSiO2 067 76 = 083. 107.1 22 Co6 20% Co, 85% ZSi0, 124 107 og2 872 102 Co 20% Co, 85% Zr, 05% Ru, 03% K/SIO, 0.90 99 088824 42 * Bor = 22 ym; catalyst particles were exacted from the slury after reaction using toluene refx YMMPSevolume mean paricle size. FAT reaction conditions: catalyst weight = ca.15 screened through 150 x 400 mesh, calcined snd reduced extemally; eemperature = 240°C; pressure = 450psig; Hy/CO ratio = 2; total low rate = 15 Umin Gems linear velociy): ‘dent, Ny = ca. 60%.b 4eaRNR Baa GUY Deas oo wasn oes D. Wei etal /Applied Catalysis A: General 210 (2001) 137-150 3 R ALO; AVIAD,. (%/micron) Cl 1 10, 100: 1000 Particle Size, D, (micron) Fig. 2. Panicle size dstibutions (PSD) of Alj03, SiO2, TiO and after (C), ultasonic anion. listed in Table 5. Although the original average part- cle sizes of the three supports were different, the per- cent decreases in VMPS still reasonably reflect the relative attrition resistances. In terms of particle size reduction, TiOz seemed a little better (but still within experimental error) than AljO3 and much better than SiO. However, AlO3 showed the best resistance to the production of fines among the three, SiOz was the weakest in attrition resistance. The differences in attrition resistance of AlOs, SiO; and TiO, should be related in part to their dif- ferent material properties (lik> Coulombic interaction and structure). In addition, the texture of the granules (also referred to as the support or catalyst particles here) and/or the connectivity between the primary particles within a granule may also play important roles. Comparing the bulk density of the supports (Table 1) with their “true” density (AlOs: 3.5-3.9, SiQp: 2.17-2.2 and TiO: 3.84/anatase; 4.26/rutile (33]) suggests that a big difference exists among the three supports in the packing of the primary particles within a granule. The attrition resistance of a granule depends strongly on the primary particle size and the interparticle spacing within the granule [34]. It has to be noted that the factors affecting the attrition resis- tance of a granule (particle) are very complicated. Be- sides the above mentioned parameters, the shape of a granule, granulation process parameters (the colloidal particle size distribution, drying temperature and rate), and the operational conditions are also of significant influence. ‘SEM images of the three supports, before and after ultrasonic attrition, are shown in Figs. 3 and 4. It can be observed that the original Al2O3 and TiO2 parti- cles were basically irregularly shaped with a lot of sharp corners and had cracks in them. SiO2 was quite spherical but also had some cracks in its outer surface. During ultrasonic attrition, it appears that protrusions of the Al,O3 and Ti2 particles were removed, so that the particles became more rounded. The presence Of fines is also noticeable, as also seen in the particle size distributions by the peak positioned below 10 um (Fig. 2). It is, therefore, suggested that the attrition of Alz0s and TiO is strongly affected by abrasion [35]. However, the attrition of SiOz would appear to bbe more dominated by fragmentation, suggested also by a displaced particle size distribution after attri- tion (Fig. 2) with mean particle size shifted largely towards smaller size (Table 5) and with fragments dis- tributed in the whole particle range (Fig. 4) [35,36], It should be pointed out that the attrition mechanism depends decisively on the relative intensity of the breaking force and the individual particle strength or toughness of the particle surface. Considering the non-uniform distribution of strength among particles or even within a single particle, it is reasonable to assume that chipping and fragmentation mechanisms were also important for AlzO3 and TiO2 during ultra~ sonic attrition as evidenced by the increase in medium sized particles (Fig. 2).Ma D. Wet et ak /Applied Catalysis A: General 210 (2001) 137-150 Table 5 I Sommary of Mirotac panicle size distibation results, before and cobalt catalysts ‘after wltasound atrition tests, forthe different supports and supported ‘Support or ‘Composition ‘Volume ‘mean particle size* Fines (<1 um) percentage” catalyst ‘Asprepued Afer auton Dewewe Asprepwed afer x) am ow @ anion (%) ‘YAl2O; (Catapal-B) —Alz03 618 45.1 27.0 0 70 Gos 20% Ca/AlOs as ar 294 ° 28 cos 2% Co, 43% Ro, 442 a 387 ° 36 10% Laj03/Ak03 couo 2H Co, 85% ZfAlnOs 828 ses ° 61 SiO; @avisor) SiO 180 “2 28 243 Cott 20% CaSi03 98 na ° a coz 20% Co, 83% ZiSiO) 18221050 ° 55 Cots 20% Co, 83% ZSiO 1208 752 ° a5 TOR? Degessa) TOs boa 907 ° 120 Coie 208 Comion RF 1217 m8 ° 21 Cons 12% Corio; a! 1513 as o2 543 Cob ‘12% ColTiO2 (RP? 103.1 75.1 0 108 "Ener = 230 *Enror = +1.0. ® Contained 97% rutile and 3% anatase. Mainly anaase. 3.3. Effect of cobalt loading Cobalt is usually the largest component in Co FT catalysts besides the support (up to 40% Co). The deposition of a large amount of cobalt oxide in the pore system and on the surface of a support might be ‘expected to have an impact on the attrition resistance of the supporvcatalyst. In order to investigate this impact, three catalysts (Co-8, Co-11 and Co-14) were prepared with 20% Co loaded on the three supports (Al203, $iO2 and TiO,). The preparation methods, physical properties of the three catalysts are summa- rized in Table 3, and their XRD patterns are presented in Fig. 1. Ultrasonic attrition was also carried out for the three catalysts. The results are illustrated in Fig. 5 and listed in Table 5, Catalyst particle morphologies were also recorded by means of SEM before and after ultrasonic attrition. The SEM photographs are shown in Figs. 6 and 7 where the bright dots on the Co-8, Co-10, and Co-11 images as well as the flaky material ‘on the Co-14 images reflect entities of mainly cobalt ‘A comparison of the change in VMPS, % fines produced, and particle size distributions of Co-8, Co-11, and Co-l4 with those of their supports (Table 5, Figs. 2 and 5) indicates that the % fines pro- duced decreased dramatically for Co-8 (CofAlz03), and Co-11 (Co/SiQ2), but was not changed much for Co-14 (Co/TiO2). The particles in the medium size range increased slightly for Co-8 and remarkably for Co-14, SEM images (Fig. 7) also show that chips and fragments in medium size range appeared for Co-8 and increased sharply for Co-14. The follow- ing is therefore suggested: (1) for Co-11 (Co/SiO2), the catalyst attrition was mainly affected by frag- ‘mentation (similar to SiOz), but the catalyst strength improved remarkably by loading cobalt; (2) for Co-8 (Co/AIz0s), the attrition of the catalyst seems to have been affected by fragmentation and chipping through which large amounts of the Co on the outer surface were removed; and (3) for Co-14 (Co/TiQz), catalyst attrition was by fragmentation as well as abrasion. It is easy to understand that the incorporation of cobalt in SiO strengthens its attrition resistance because, uring the drying and calcination process, the cobalt ‘oxide can concentrate at the connection points or the small gaps between the primary SiOz particles (37] within the granule and eventually improve its con- nectivity. In addition, the strong interaction betweens uy or e ot 38 Bee oeYr Ty st It It © q D. Wei et al /Applied Catalysis A: General 210 (2001) 137-150 M45 Fig. 3. SEM photographs ofthe calcined AlOs, SiOz, and TiO (rutile) supports cobalt and SiO> [38,39] should have a positive effect on the catalyst atrtion resistance. However, for Co-8 and Co-14, itis hard to understand how fragmentation became more significant since the supports themselves were hard enough to resist fragmentation originally. A. comparison of the VMPS and particle morphologies of Co-8 and Co-14 (Table 5, Fig. 6) with those of their supports (Table 5, Fig. 3) suggests that agglomeration of catalyst particles may have occurred during catalyst preparation, This kind of agglomerates may not have been strong enough to resist the breaking force in the ultrasonic field. Based on this, the percent decreases in volume mean particle size (VMPS) of Co-8 and Co-14 (Table 5) may not reflect the “true” attrition resistance6 D. Wel et ak /Applied Catalysis A: General 210 (2001) 137-150 Fig. 4. SEM photographs of the ultrasonically sted AlLOs, SiO, and TiO> (rutile) supports of the catalyst particles. It should also be noticed that, due to the very low BET surface area (Table 1), a large amount of cobalt was deposited on the outer surface of the TiO» particles (the white flaky materials ‘on the particle surfaces in Figs. 6 and 7 as determined by EDX). As reflected by the similar concentration of fines obtained for the support and the catalyst (Table 5), this surface enrichment did not improve its resistance against abrasion. However, the impreg- nation of cobalt on AlsOs did improve its resistance against abrasion. This can tentatively be related to strong interaction between cobalt and Alas [40,41] ‘The existence of cobalt oxide particles may have changed the surface tension of the AlaOs particles andLo D. Wei etal /Applied Catalysis A: General 210 (2001) 137-150 147 aVIaD, (*olmieron) Particle Size, D, (micron) Fig. 5. Particle size distributions (PSD) of Co-8 (CofA 02), Co-10 (Co-ZAK03), Co-11 (ColSi02), and Co-14 (ColTIO,): before (®), and after (CD, ulsasoaic atition. could therefore have altered their resistance against chipping. 3.4, Effects of promoters and preparation methods Supported cobalt FT catalysts may contain one or ‘more types of promoters: e.g. a reduction promoter, such as Ru, and/or a chemical promoter, such as Zr and La. In this study, a number of catalysts were pre- pared with various promoters and/or using different preparation methods with the purpose of investigat- ing the effects of promoters and preparation method on catalyst attrition resistance. For the Co/AlO3 system, Ru-La and Zr Were introduced separately (Co-9 and Co-10). A comparison of the fines pro- duced with Co-8, Co-9 and Co-10 (Table 4, Fig. 5) suggests that the addition of Zr diminished slightly the catalyst attrition resistance. But, the addition of RuLa seemed to have no significant effect on cata- lyst attrition resistance. This can probably be related to the difference in the loadings and/or the locations of the promoters in the catalyst. An elemental anal- ysis by EDX indicated a higher Zr concentration on the outer surface of the catalyst particles (the white flaky materials on the surface of Co-10 particles in Figs. 6 and 7). This was also evidenced by chemical analysis of the attritted fines of Co-10 in which the content of Zr was much higher than in the bulk parti- cles (21.4 versus 3.4%). The Zr layers were probably not strongly connected to the AlzOs surface and were easily removed from the particle surface to form fines during attrition (Co-10 in Figs. 6 and 7). 6-12 and Co-13 had the same composition but were prepared using different methods. Their BET surface areas and bulky densities were very close (Table 3). The data given in Table 5 suggests only a small effect of preparation method on attrition resis- tance. The difference in attrition resistance between the two TiO-supported catalysts (Co-15 and Co-16) ‘could be reasonably attributed to the big difference in strength between the two types of TiOz (rutile versus anatase) [22] regardless of their different preparation methods. 4, Summary Our findings may be summarized as follows: AlOs- and SiOz-supported Co F-T catalysts en- countered noticeable attrition in the SBCR runs, but ‘AlOs-supported catalysts showed significantly bet- ter attrition resistance. The attrition resistance of the three commonly used supports (Al203, SiOz and TiOz/rutile) varied greatly. AlO3 was found to be the best in terms of producing the least fines. SiOz wwas less attrition resistant than the others. Loading of cobalt improved the attrition resistance of SiOz and AlnOs, but no evident improvement was observed for TiOz. 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