Original Proposal Summary

Transcription

1 Designing nanostructured heterogeneous catalysts to exploit pulsing in gas-liquid packed bed reactors M. J. McCready E. J. Maginn University of Notre Dame Chemical and Biomolecular Engineering Original Proposal Summary This proposal describes work that is intended to develop new nanostructured catalysts for gas-liquid reactions, which have a system of macro pores designed to take advantage of oscillatory convection that can be created by large scale hydrodynamic disturbances. Thus we are combining a nanoscale structure that provides the best reaction environment with a macroscale structure that provides the highest possible mass transfer rates. The net effect is a new catalyst that can lead to reductions in volume of gas-liquid packed bed reactors (a.k.a. "trickle" beds) by an order of magnitude or more because active, useful metal could be placed throughout the pellet rather than just at the surface as is typical for gas-liquid reactions. Porous silica structures having both a nanopore network (radius nm) and a macropore network (radius ~0.2 mm) will be synthesized. The nanopores will be created using a surfactant-mediated templating process, while the macropores that span the entire pellet will be added through use of sacrificial fibers. The silica material will be impregnated with platinum to make it catalytically active for a test 41

2 reaction of phenylacetylene plus hydrogen going to styrene and then to ethylbenzene. These pellets will be used in a recycle reactor that uses a novel catalyst configuration that our previous work has shown can clearly differentiate the mass transfer effects of pulsing flow compared to trickling flow at the same gas and liquid flowrates. The spanning network of macro pores will enable convective mass transfer within the pellet, in the pulsing flow regime, because it will take advantage of Taylor-Aris oscillatory transport mechanism. That is, the pressure fluctuations associated with the pulses, will cause an oscillatory flow within the macropores. If the macropore diameter is chosen correctly for a given pulsing frequency, the time scale for radial diffusion and axial transport will match, leading to a reduction in diffusion distance from the pellet radius to just the macropore radius -- about an order of magnitude. This study will comprise synthesis of this novel catalyst, mass transfer studies in trickle and pulsing flow to prove the enhancement mechanism and reaction studies to demonstrate the increased activity per unit reactor volume. The net effect is that the length of packed bed reactors for gas-liquid reactions could be greatly reduced with our new catalyst structure. The benefits of such a result would be a considerable reduction in capital costs for full-scale plant retrofits and new construction, increased application of gas-liquid packed bed reactors for "closet scale" distributed production for chemicals that are hazardous to transport and possible use of this reaction scheme for reforming or other types of fuel conversion on board motor vehicles. 42

3 The proposed work should impact the general problem of how to best exploit the increasing potential of nano synthesis techniques to produce more active and selective catalysts by addressing the mass transfer limitations, which are particularly acute in gas-liquid reactions. It should encourage similar studies to look for links between nanostructured materials for separation processes and the fluid dynamics of these devices. Much of the information below is contained in a thesis by N. S. Martino: Hydrodynamics of a two-dimensional gas-liquid packed bed. Notre Dame Library. Activities Synthesis of Catalyst Support The synthesis of mesoporous silica as a catalyst support is based on the techniques used by Nooney et al. (2001). It was scaled up to attempt to produce the catalyst faster. The following describes the experimental procedure used to produce both the macroporous and non-macroporous catalyst supports. Several attempts were made before a useable material was found. A full description of the experiments can be found in the APPENDIX which is attached below. Only a successful run will be detailed here. The chemicals used in this synthesis were purchased and used as received from Sigma-Aldrich. 4.5 g of cetyltrimethylammonium bromide (CTAB) is divided into three groups of 1.5 g. Each of these individual groups is then dissolved in separate beakers containing g of deionized water each (total deionized water equals 250 g). A Fisher Scientific sonicater is used to speed up the dissolution. Once dissolved these solutions are mixed together with 19.3 g of 2 molar NaOH in the reactor. This 43

4 brings the ph of the solution to about Then 18.5 g of tetrabutyl orthosilicate (TBOS) is added drop wise to the solution while it is stirring. The reaction is then allowed to stir for 24 hours. The product of this reaction is a viscous gel of silica. This gel is removed from the reactor and washed with water. It is then broken up and molded into spheres of approximately 5-6 mm in diameter. Half of these spheres are then stuck with a minimum of 10 cellulose fibers of approximately 0.2 mm in diameter (sisal fibers provided by International Fiber Corporation). Then all of the spheres are allowed to dry in atmosphere for 24 hours before calcination. It is important to note the chemistry that occurs to form the mesoporous silica. The silica source, TBOS, forms an emulsion when mixed with water. CTAB is a surfactant that has a hydrophobic tail and a hydrophilic head. Because of this it buries its hydrophobic tail inside the TBOS drop leaving its head exposed to the water. The presence of a base will accelerate this action along the water emulsion interface creating a long rod. These rods pack hexagonally and form a sphere from the emulsified drop of TBOS. The silica begins to grow along the TBOS water interface and eventually grown into the bubble. Spheres form under the proper reaction conditions but Nooney et al. (2001) showed that by altering the conditions a multitude of products can be formed. 3.7 Removal of Template and Sacrificial Fibers The product of the synthesis reaction is not porous until the CTAB template is removed. This can be done either by chemical extraction or by thermal means. Both are effective ways to leave a highly porous silica structure. Calcination was chosen 44

5 for this work because it can be used to remove the template and the sacrificial fibers in one step. After being allowed to dry at atmospheric conditions the spheres were calcined in a furnace controlled by an Omega temperature controller. The temperature was ramped up at 1 o C per minute to 620 o C under flowing oxygen. The slow ramp rate was used to avoid any cracking of the silica due to stress. It was then held at that temperature for 10 hours to ensure complete burn out of the CTAB template and the sacrificial fibers. Finally the samples were brought back down to room temperature over 6 hours. It should be noted that there was no structural difference between samples that were calcined after being dried at atmospheric conditions compared to those that were calcined after being dried in a vacuum furnace at 100 o C to remove water. 3.8 Platinum Impregnation After the mesoporous silica was made porous by calcination it needed to be impregnated with platinum to make it an active catalyst. The procedure used was identical to the one presented by Long and Yang (1998) who were able to impregnate MCM-41 with up to 5 percent by weight platinum. Incipient wetness impregnation method was used with hydrogen hexachloroplatinate (IV) hydrate 99.9%. After initial impregnation by the salt, the samples were dried in atmospheric conditions for 24 hours. To reduce the platinum the samples were then calcined at 400 o C for at least 5 hours in 5.34% H 2 in N Hydrogenation of Phenylacetylene Four experiments were run to test this novel catalyst. For each experiment the catalyst was placed in the upper or lower packing configurations. Figure 3.6 shows a 45

6 schematic of the packing configurations used. The macroporous catalyst was run in one time in the upper and one time in the lower configuration. This was repeated for the non-macroporous catalyst. One liter of tetradecane solvent and 1 ml of decane GC international standard are added to the reservoir. The liquid is then circulated for several minutes to assure complete wetting of the catalyst. Nitrogen is passed through the gas loop for 15 minutes to remove any air that may have become trapped inside. Once the gas loop was purged and the catalyst were wetted, phenylacetylene was introduced by syringe and the reactor was sealed. The nitrogen in the gas loop is then purged with hydrogen followed by opening the gas loop up to the reactor. Additional hydrogen was added to the system to compensate any losses from reaction. Samples were taken of the liquid phase at regular intervals and stored for later analysis. The reaction is terminated by turning off the pump and hydrogen supply and purging the system with nitrogen. 46

7 Figure 3.6: Representation of different column packing placement used for testing catalyst Mesoporous Silica Catalyst Support Each batch of viscous gel from the reactor was rolled into spheres with a diameter of 0.5 to 1 cm. Half of these spheres were randomly selected to have fibers inserted in them. Figure 4.34 shows a sample of the dried spheres before calcination. After calcination the spheres decreased to about half of their original size mostly due to the 47

8 loss of entrapped water. Figure 4.35 shows a group of pellets after calcinations. As it can be seen the pellets have an outside diameter ranging from 3 to 5 mm. Calcination was used to remove the CTAB template from the silica spheres leaving a porous catalyst support. The surface area of the calcined pellets was determined using nitrogen adsorption and the Brunauer Emmett Teller (BET) equation. It was determined to be 530 m 2 /g. The surface area was measured again after the test reaction and found to be 330 m 2 /g. This shows the unstable porosity of the mesoporous silica. An optical microscope with a digital camera attached was used to take a photograph of the surface of one of the pellets with macropores in it. This can be seen in Figure The photograph was calibrated and a length scale was attached. Figure 4.36 shows three macropores on the surface of the pellet. The diameter of these pores ranges from about 0.2 to about 0.4 mm. This shows that the pore size in the range that enhancement is expected. Only the macropores can be seen since the mesopores are too small to be viewed with a standard optical microscope. 48

9 (a) (b) Figure 4.34: Dried silica spheres used as catalyst support (a) spheres with no fibers inserted (b) spheres with sacrificial fibers inserted to make the macropores Figure 4.35: Mesoporous silica catalyst support after calcinations 49

10 Figure 4.36: Magnification of the surface of a macroporous silica catalyst support Platinum Impregnation of Mesoporous Silica Catalyst Support After calcination, the catalyst was stored under nitrogen until enough was calcined to run eight reactions (2 each of macropore pulsing, macropore trickling, no macropore pulsing, and no macropore trickling). Then each group was impregnated and reduced together. This was stored under nitrogen until it was used for the test reactions. Platinum dispersion was measured using hydrogen adsorption. Microbursts of hydrogen were injected into the sample and the exit concentrations of hydrogen were measured. This was performed on a random sample twice for reproducibility. The platinum dispersion was measured at 2.31%. This shows that there are large platinum crystals on the surface and that much of the platinum on the catalyst was unavailable for reaction. Even though there was a low platinum dispersion the reaction did 50

11 commence and conversions of up to 50% were accomplished within a reasonable time. These results will be presented in the following section. Findings Support for the catalyst was made out of mesoporous silica. Spherical pellets of approximately 5 mm to 10 mm diameter were molded out of a viscous gel of mesoporous silica. Half of the pellets had cellulose fibers inserted in them. After calcinations the pellets shrunk to about 3 mm to 5 mm in diameter. The loss in size was mostly due to the loss of water from the pellet. The cellulose fibers left macropores on the order of 0.2 mm. The surface are of the pellets was 530 m 2 /g after calcination but measured 330 m 2 /g after the test reactions. Platinum was used as the active material and was placed on the support using incipient wetness. The dispersion of platinum was measured at 2.31%. Test of Catalyst Using the Hydrogenation of Phenylacetylene For each of the four test reactions run, dimensionless concentration profiles as a function of time were made, where the dimensionless concentration was equal to the component concentration divided by the initial phenylacetylene concentration. From the decay of phenylacetylene concentration the initial rates of reaction can be calculated and compared for each of the four cases. Figure 4.37 shows the concentration profile for the first reaction run, no macropores in the trickling regime. This reaction had the best performance of all four test reactions and reached a conversion of almost 50% in 36 minutes. The reaction results for catalyst with no 51

12 macropores in the pulsing regime can be seen in Figure This figure shows an obvious decrease in reaction performance over the same time period compared to the trickling reaction. This result is unexpected and was the first sign that the catalyst used may not be reliable for experimentation. Figure 4.39 shows the reaction using catalyst with macropores in the trickling flow regime. This reaction is supposed to be comparable to the other trickling reaction but as it can be seen it more closely compares to the pulsing reaction run with non-macroporous catalyst. The results of the fourth reaction can be seen in Figure This reaction was run with macroporous catalyst in the pulsing regime. Large enhancements in reaction rate were expected but not seen. In fact, this reaction again shows a poorer performance for the pulsing regime compared to the trickling regime. Degradation of the catalyst over time could be the major cause behind this type of behavior. 52

13 Figure 4.37: Reaction concentration profile as a function of time for non-macroporous catalyst placed in the trickling flow regime Figure 4.38: Reaction concentration profile as a function of time for non-macroporous catalyst placed in the pulsing flow regime 53

14 Figure 4.39: Reaction concentration profile as a function of time for macroporous catalyst placed in the trickling flow regime Figure 4.40: Reaction concentration profile as a function of time for macroporous catalyst placed in the pulsing flow regime 54

15 A comparison of the initial rates of reaction for each of the four experiments can be seen in Figure This shows the concentration profiles for phenylacetylene with time. It gives a clearer picture of the unpredictable reaction performance of the catalyst. Table 4.3 shows the initial rates of reaction for each of the four reactions run. The initial rate of reaction was calculated by fitting a line to the data to get the rate of decay of phenylacetylene as a function of time. Figure 4.41: The decay of phenylacetylene as a function of time for each of the four reactions 55

16 Table 4.3: Initial rates of reaction for each of the four test reactions Packing Set Up Initial Rate of Reaction, mol/(l min) No Macropores, Trickling 4.84 * 10-4 No Macropores, Pulsing 3.16 * 10-4 Macropores, Trickling 2.92 * 10-4 Macropores, Pulsing 2.72 * 10-4 Although the catalyst used for the tests was able to achieve up to 50% conversion within 1 hour, overall it showed unreliable performance. The trickling regime always showed increased initial reaction rates when compared to the pulsing regime. The lowest initial rate of reaction was mol/(l min) and was for the macroporous catalyst in the pulsing regime. The highest initial rate was seen for the nonmacroporous catalyst run in the trickling regime, it was mol/(l min). Discussion A novel macroporous catalyst was created to take advantage of the pressure fluctuations in the pulsing flow regime. This catalyst uses the pressure fluctuations to reduce the mass transfer resistance to its internal active sites. It was expected to exhibit increased reaction rates when compared to a non-macroporous catalyst made of the same material but it did not. 56

17 Two problems could have contributed to the situation. First a lot of experimentation went into making a gel phase that could be formed into cm size pellets and into which fibers could be inserted. Further it was necessary that the pellets which result after calcinations have sufficient mechanical stability to stand up to reaction conditions. We were able to accomplish these goals. Unfortunately this was at the expense of much of the meso-porosity. The low dispersion of Pt indicates that the final product was not a very active catalyst. A second problem could have been that the pressure fluctuations that occurred in the pulsing regime were not strong enough to cause the necessary oscillatory flow within the pellets to achieve the reaction enhancements. So while no reaction enhancement occurred, we are not certain that it would not occur in a much larger reactor (perhaps 10 cm in diameter instead of 2 cm) which could generate larger pressure fluctuations. Unfortunately, making the catalyst is very labor intensive and producing enough for our small reactor was already difficult. References: Nooney, R.I., M. Kalyanaraman, G. Kennedy, and E.J. Maginn, Heavy Metal Remediation Using Functionalized Mesoporous Silicas with Controlled Macrostructure, Langmuir, 17: ,

18 APPENDIX A.1 Determination of Proper Pore Size For good enhancement the dimensionless frequency (b) needs to be greater than or equal to 10 (Leighton and McCready Figure 2, 1988) 1/ 2 Ê ˆ b = aá w (A.1) Ë D a = PoreRadius, m w = Frequency, radians / s = 2p (corresponds to 1 Hz, typical value in reactor used) D = Diffusivity, m / s = m / s (Wilhite et al., 2001) a = b Èw Í Î D 1/ 2 (A.2) 10 a = (A.3) 1/ 2 È 2p Í Î a = m = 0.2 mm (A.4) It should be noted that pore sizes larger than this will also experience transport enhancement but due to the particle size pore sizes around 0.2 mm are the best choice. A.2 Catalyst Support Reaction Results The following table shows general results for the variety of attempts to make the catalyst support. For each attempt the procedure explained in CHAPTER 3, Section 3.6 was used. Tables A.1-A.30: Results for various attempts to make catalyst support sorted by date 58

19 H 2 O (g) Temperature ( o C) 18 CTAB (g) 4.50 Stir Rate (rpm) 200 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 1.16 Date 11/30/01 Results: Too many fibers, light coating formed in needles around fibers H 2 O (g) Temperature ( o C) 25 CTAB (g) 4.50 Stir Rate (rpm) 275 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 12/18/01 Results: Gel like, did not hold together H 2 O (g) Temperature ( o C) 25 CTAB (g) 4.50 Stir Rate (rpm) 300 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 1/16/02 Results: Wax like material stuck on side of reactor, low yield of irregularly shaped particles (2-3 cm), very brittle after drying H 2 O (g) Temperature ( o C) 25 CTAB (g) 4.50 Stir Rate (rpm) 350 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 1/17/02 Results: Total yield was wax like structure stuck to the side of the reactor, dried very brittle H 2 O (g) Temperature ( o C) 25 59

20 CTAB (g) 4.51 Stir Rate (rpm) 175 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 1/20/02 Results: Wide size range of irregularly shaped particles (1 mm 1 cm), disk like, dried hard H 2 O (g) Temperature ( o C) 25 CTAB (g) 4.50 Stir Rate (rpm) 175 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 1/27/02 Results: Low yield of irregularly shaped spheres (~ 1 cm diameter), mostly gel stuck to reactor, brittle upon drying H 2 O (g) Temperature ( o C) 25 CTAB (g) 4.50 Stir Rate (rpm) 200 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 1/28/02 Results: Wide size range of irregularly shaped particles (1 mm 1 cm), disk like, dried hard H 2 O (g) Temperature ( o C) 25 CTAB (g) 4.50 Stir Rate (rpm) 250 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 2/2/02 Results: Sludge, some stuck to walls, breaks apart upon drying H 2 O (g) Temperature ( o C) 25 60

21 CTAB (g) 4.50 Stir Rate (rpm) 220 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 2/3/02 Results: Large ball of sludge, much like the sludge used to make the support used for experimentation but its use was not realized at the time H 2 O (g) Temperature ( o C) 35 CTAB (g) 4.50 Stir Rate (rpm) 200 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 2/5/02 Results: Extremely low yield of large spheres ~ 1.5 cm diameter H 2 O (g) Temperature ( o C) 15 CTAB (g) 4.50 Stir Rate (rpm) 200 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 2/6/02 Results: Spheres of approximately 3 mm diameter, stuck together as soon as pulled out of solution H 2 O (g) Temperature ( o C) 15 CTAB (g) 4.50 Stir Rate (rpm) 200 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 2/9/02 Results: Attempt to reproduce spheres of 2/6/02 and try to separate them, stuck together could not be separated H 2 O (g) Temperature ( o C) 15 61

22 CTAB (g) 4.50 Stir Rate (rpm) 200 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 2/12/02 Results: Large amount of viscous sludge H 2 O (g) Temperature ( o C) 15 CTAB (g) 4.40 Stir Rate (rpm) 230 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 2/15/02 Results: Clay-like sludge, stuck to side of reactor H 2 O (g) Temperature ( o C) 20 CTAB (g) 4.50 Stir Rate (rpm) 230 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 2/16/02 Results: Low yield, all stuck to sides of reactor, powder-like H 2 O (g) Temperature ( o C) 15 CTAB (g) 4.50 Stir Rate (rpm) 200 NaOH (g) ph 12.8 TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 3/27/02 Results: Viscous gel, first attempt at molding, did not seem hard enough to use in reactor H 2 O (g) Temperature ( o C) 15 62

23 CTAB (g) 4.50 Stir Rate (rpm) 200 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 3/29/02 Results: Viscous gel, very brittle after drying H 2 O (g) Temperature ( o C) 15 CTAB (g) 4.51 Stir Rate (rpm) 200 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 4/2/02 Results: Approximately 3 mm diameter spheres, dried very hard, shrunk upon drying and calcinations, lost over 1/2 of initial size H 2 O (g) Temperature ( o C) 15 CTAB (g) 4.51 Stir Rate (rpm) 175 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 4/9/02 Results: Large diameter particle, upwards of 1 cm diameter upon drying, much size variance, brittle after drying H 2 O (g) Temperature ( o C) 15 CTAB (g) 4.50 Stir Rate (rpm) 200 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 3/29/02 Results: Viscous gel, very brittle after drying H 2 O (g) Temperature ( o C) 15 63

24 CTAB (g) 4.49 Stir Rate (rpm) 135 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 4/18/02 Results: Attempt to make spheres that will be large enough after drying, a useless low viscosity gel that could not be separated from solution H 2 O (g) Temperature ( o C) 15 CTAB (g) 4.51 Stir Rate (rpm) 150 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0.08 Date 4/23/02 Results: Attempt to get fibers in spheres, some spheres formed with fibers entrapped, became extremely brittle after calcination H 2 O (g) Temperature ( o C) 15 CTAB (g) 4.51 Stir Rate (rpm) 150 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0.11 Date 4/24/02 Results: Powdery gel with fibers in it, could not be molded, dried extremely brittle H 2 O (g) Temperature ( o C) 15 CTAB (g) 4.50 Stir Rate (rpm) 160 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0.11 Date 4/30/02 Results: Extremely small spheres with no fibers entrapped, fibers in bottom of reactor with small amounts of gel on them H 2 O (g) Temperature ( o C) 15 64

25 CTAB (g) 4.50 Stir Rate (rpm) 150 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0.10 Date 5/7/02 Results: Mostly gel, a few irregularly shaped particles, dried extremely brittle H 2 O (g) Temperature ( o C) 15 CTAB (g) 4.50 Stir Rate (rpm) 110 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) /9/02 Results: Crystal like low viscosity gel, could not be separated from solution H 2 O (g) Temperature ( o C) 25 CTAB (g) 4.51 Stir Rate (rpm) 150 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0.12 Date 5/7/02 Results: Viscous gel with fibers entrapped, molded, very brittle after calcination H 2 O (g) Temperature ( o C) 20 CTAB (g) 4.50 Stir Rate (rpm) 150 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0.12 Date 5/15/02 Results: Lower viscosity gel than 5/7/02, again extremely brittle after calcination H 2 O (g) Temperature ( o C) 25 65

26 CTAB (g) 4.50 Stir Rate (rpm) 150 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0 Date 5/21/02 Results: Attempt to see if leaving fibers out makes a stronger material but still brittle after calcinations H 2 O (g) Temperature ( o C) 25 CTAB (g) 4.50 Stir Rate (rpm) 150 NaOH (g) ph TBOS (g) Reaction Time (hr) 24 Fibers Added (g) 0.10 Date 5/7/02 Results: Viscous gel, molded, attempted to use aluminum wire as support to add strength, still brittle after calcinations 66