37...: 93.! .215: :,....u.: .8...“ . . K ‘1! ix .: fl .. tint-‘1...- _. I:l. . r)! . x\ ’5‘ 55'. -1\.. I: . :1: .9! t I. ,dyanwb . .. u. 2.... 4 pl.» . .55915 | x 9.0.: ‘Ailfi‘ .1... A~ a t .1 ‘v .25. 1.4 17. xiii...‘ . .3503... \ Ya»: I: t 1.. 0.; . . 9. , .D . V . Va 0,! r3: .. r I: \v 2.: u. :l‘ A .. . 1.1.4 1.»..‘xlilftv. ‘ i .. (I \n 11...... 3:11.. $....:. .9. . ‘ é! a! f .. .v {3.1-1.33 , I .h.n.,u . .21 I! n «x... tWfiIVKLHFV ..t.r..;swV unfit V . . a .. . . '31.»); .‘ vv . r to. v.3- . .7 r3! , ~y . 5.1.: a .rnrul , l. mulch-f 51’. I. u. ‘ Date MllllllillHlllNlllllllllllHllllllllllllllllllllllillllllfl 31293 01037 3631 This is to certify that the thesis entitled Catalysts and Supports for Conversion of Lactic Acid to Acrylic Acid and 2,3-Pentanedione presented by Robert H. Langford has been accepted towards fulfillment of the requirements for CHE 1" 5 ° degree in V Majoérofessor 10/20/93 0-7639 MS U is an Affirmative Action/Equal Opportunity Institution LIBRARY Mlchlgan State University PLACE ll RETURN BOX to remove this checkout from your record. To AVOID FINES rotum on or baton date duo. DATE DUE DATE DUE DATE DUE i—T—i MSU to An Nflmottvo Won») Opportunity lnotltmlon ] CATALYSTS AND SUPPORTS FOR CONVERSION OF LACTIC ACID TO ACRYLIC ACID AND 2,3-PENTANEDIONE 3? Robert a. Langford Jr. A THESIS Submitted to Michigan state University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Chemical Engineering 1993 Dennic J. Miller, Advisor ABSTRACT CATALYSTS AND SUPPORTS FOR CONVERSION OF LACTIC ACID TO ACRYLIC ACID AND 2,3-PENTANEDIONE BY Robert H. Langford Jr. Reactions of vapor-phase lactic acid over various supports and supported catalysts were studied to maximize the production of acrylic acid and 2,3-pentanedione. A 34 wt% aqueous lactic acid solution was vaporized and passed over a catalyst bed which was positioned in a vertical, down-flow packed bed reactor. Condensible product analysis was accomplished with a varian 3700 Gas Chromatograph with FID detection, while non-condensibles were analyzed with a Varian 3300 Gas Chromatograph which used thermal conductivity for detection. Extensive catalyst/support microporosity causes lactic acid cracking and increases acetaldehyde production, and thus should be avoided. The XDC 005 silica support impregnated with NazfiAsm gave a 2,3-pentanedione yield of 23.3% with 67.5% selectivity at 300'C. The best acrylic acid yield (22.7%) was found with the same support impregnated with NaNOs at a reaction temperature of 350'C. Although these are promising results, much more work is necessary for this project to produce a marketable system. This work is dedicated to my mother, Mrs. Myrna Langford, and to my loving and supportive family. iii ACKNOWLEDGEMENTS The author wishes to thank Dr. Dennis J. Miller for his support and guidance throughout the course of this project; Dr. James E. Jackson, for his suggestions and comments; Mr. Garry C. Gunter, for access to his data, methods and knowledge of the subject matter; and Mr. Johnathan P. Grow and Mr. Timothy Carlson, for their work with calcium hydroxyapatite. iv TABLE OF CONTENTS LIST OF TABLES LIST OF FIGURES 1. INTRODUCTION AND BACKGROUND 2. EXPERIMENTAL METHODS 2.4 2.5 2.6 Materials Catalyst Preparation Reactor Configuration Product Collection Product Analysis Typical Procedure 3. BIOMINERAL-DERIVED CALCIUM HYDROXYAPATITE 3.4 3.5 3.6 Introduction Calcium Hydroxyapatite Properties Catalyst Preparation Catalyst Characterization Effects of Calcination Temperature Particle Size Study 4. CARBON SUPPORTS 4.1 4.2 Strem Activated Carbon Cherry-derived Carbon Charred Cherry Pits Carbograph Carbons v PAGE vii 12 13 14 18 19 19 21 23 37 45 52 54 58 4.5 Summary SILICA SUPPORTS 5.1 Glass Beads 5.2 Silica Gel 5.3 Spherosil Supports CATALYST SURVEY DISCUSSION AND CONCLUSIONS 7.1 Mass Balance Considerations 7.2 Mechanistic Considerations 7.3 Conclusions LIST OF REFERENCES APPENDIX vi 62 67 70 75 83 99 105 106 110 112 LIST OF TABLES Supports studied Catalysts studied Normal Reactor Operating Parameters Calcium Hydroxyapatite Properties Calcium Hydroxyapatite Results at 300°C Calcium Hydroxyapatite Results at 320'C Calcium Hydroxyapatite Particle Size Study Results Carbon Support Reaction Parameters Carbon Support Results for 300'C Carbon Support Results for 320'C Reaction Parameters for the silica supports Calcination Temperature vs. Surface Area Spherosil Silica Results at 300 and 320'C Catalyst Reaction Parameters Catalyst Survey Results at 280'C Catalyst Survey Results at 300°C Catalyst Survey Results at 320'C Catalyst Survey Results at 350'C pH Results GC Response Factors Pseudo-Run Results Carbon Error Trends vii PAGE 17 20 33 34 42 48 65 66 69 72 82 89 95 96 97 98 100 101 104 105 - A.10 A.11 A.12 A.13 A.14 A.15 A.16 A.17 A.18 A.19 A.20 A.21 Results for at 300‘C Results for at 400°C Results for at 500'C Results for at 600’C Results for at 700°C Results for at 800'C Results for Calcium Calcium Calcium Calcium Calcium Calcium Calcium mesh particle size Results for Calcium mesh particle size Hydroxyapatite Hydroxyapatite Hydroxyapatite Hydroxyapatite Hydroxyapatite Hydroxyapatite Hydroxyapatite Hydroxyapatite Results for Calcium Hydroxyapatite mesh particle size Results for Results for Results for Results for Results Results for Results for Results for Results for Results for Results for Results for for- Strem Activated Carbon Na3P04 on Strem Carbon calcined calcined calcined calcined calcined calcined 10 X 16 16 X 30 30 x 60 the Activated Cherry Carbon the Charred Cherry Pits Na3P04 on the Cherry Char Carbograph 1 Carbograph 2 the 1 mm diameter glass beads the Silica Gel the Calcined Silica Gel the XOA the XOB 400 Silica 030 Silica viii 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 A.22 A.23 A.24 A.25 A.26 A.27 Results for the XOC 005 Silica Results for the XOC 005 Silica (short residence time) Results for NaOH on the XOC 005 Silica Results for Na3P04 on the XOC 005 Silica Results for NaN03 on the XOC 005 Silica Results for Nazt‘IAsO4 on the XOC 005 Silica ix 139 140 141 142 143 144 LIST OF FIGURES Lactic Acid Conversion Pathways Reactor system Typical GC Chromatogram Average Pore Size vs. Calcination Temperature for Calcium Hydroxyapatite Delta pH vs. Calcination Temperature for the Calcium Hydroxyapatite Delta pH vs. Particle Size for the Calcium Hydroxyapatite Absolute Product Yields vs. Temperature for the Calcium Hydroxyapatite calcined at 300°C Absolute Product Yields vs. Temperature for the Calcium Hydroxyapatite calcined at 400°C Absolute Product Yields vs. Temperature for the Calcium Hydroxyapatite calcined at 500°C Absolute Product Yields vs. Temperature for the Calcium Hydroxyapatite calcined at 600°C Absolute Product Yields vs. Temperature for the Calcium Hydroxyapatite calcined at 700°C Absolute Product Yields vs. Temperature for the Calcium Hydroxyapatite calcined at 800°C Absolute Product Yields vs. Temperature for the 10 x 16 mesh Calcium Hydroxyapatite Absolute Product Yields vs. Temperature for the 16 x 30 mesh Calcium Hydroxyapatite Absolute Product Yields vs. Temperature for the 30 x 60 mesh Calcium Hydroxyapatite PAGE 10 15 22 24 25 27 28 29 30 31 32 38 39 40 Absolute Product Yields vs. Temperature for the Strem Activated Carbon Product Selectivities for the Strem Activated Carbon - Reaction Temperature 300°C Absolute Product Yields vs. Temperature for Na3P04 on the Strem Carbon Absolute Product Yields vs. Temperature the Activated Cherry Carbon Absolute Product Yields the Charred Cherry Pits Absolute Product Yields Na3P04 on Charred Cherry Pits Absolute Product Yields Carbograph 1 Absolute Product Yields Carbograph 2 Product Selectivities for Carbograph 2 - VS. VS. VS. Temperature Temperature Temperature for for for for vs. Temperature for Reaction Temperature 300'C Absolute Product Yields 1 mm Glass Beads Absolute Product Yields Silica Gel Absolute Product Yields Calcined Silica Gel Absolute Product Yields the XOA 400 silica Absolute Product Yields the X08 030 silica Absolute Product Yields the XOC 005 silica Absolute Product Yields the XOC 005 silica Absolute Product Yields NaOH on XOC 005 silica VS. VS. VS. VS. VS. VS. VS. VS. xi Temperature Temperature Temperature Temperature Temperature Temperature Temperature Temperature for for for for for for for for 46 50 51 53 55 57 59 61 63 68 71 74 76 78 80 84 85 Absolute Product Yields vs. Temperature for Na3P04 on the XOC 005 silica Absolute Product Yields vs. Temperature for NaNOs on the XOC 005 silica Absolute Product Yields vs. Temperature for Na2HA504 on the XOC 005 silica Product selectivity of Na3P04 on XOC 005 silica - Reaction Temperature 320°C Product selectivity of NaN03 on XOC 005 silica - Reaction Temperature 320°C Product selectivity of NaznAso‘ on XOC 005 silica Reaction Temperature 300°C Pore Distribution 300°C Pore Distribution 325°C Pore Distribution 400°C Pore Distribution 600°C Pore Distribution 700°C Pore Distribution 800°C xii 86 87 88 91 92 94 112 113 114 115 116 117 CHAPTER 1 INTRODUCTION AND BACKGROUND Lactic acid (2-hydroxy-propanoic acid) is an optically active molecule that is used as a food additive and in textile production (1). It has been traditionally used in limited quantities (40-50 MM lb/yr) at a price of 0.60 to 1.00 $/lb but it is undergoing a surge in production via efficient starch-based fermentation processes (1). This is giving lactic acid potential applications in biodegradable polylactide polymers (2). The new production technologies have a decreased cost associated with them which suggests that lactic acid could become a major biomass-based feedstock in the near future. The projected production capacity and cost for 1996 are 300+ MM lb/yr and 0.25 to 0.35 $/lb, respectively. Lactic acid's structure allows it to exist in various forms. The lactic acid molecule has an asymmetric carbon atom, therefore it is capable of existing as the d- or 1- forms. Both forms of lactic acid form esters and salts readily. Reactions of vapor-phase lactic acid over various supports and supported catalysts are the focus of this study. The primary pathways of lactic acid conversion are shown in Figure 1.1: pathways to acrylic acid and to 2,3-pentanedione are the desired routes of reaction. ILactic acid conversion to Primary Catalytic Reaction Pathways of Lactic Acid 0 ”Becamenylation‘ /u\ + C0 + H20 Dccarboxylatior H + (302 + H2 Acctaldchydc . Dehydration ; / OH + H20 HO . ' Acrylic O we. ._, A. Lacnc O . . Prepanoic Acid 0 .,_~-- (3 -Pc°m°" 3’“ + co2 + ZHZO O 2,3-Pcntanedionc Figure 1. 1 - Lactic Acid Conversion Pathways 3 acrylic acid is accomplished through direct dehydration, which has long been of interest as a potential route to polymers from biomass. However, selectivity to this pathway has not been high enough to make commercialization feasible. Current demand for acrylic acid is approximately 2 x 109 lb/yr with major applications being polyacrylate esters, superabsorbing polymers and detergents (2). Lactic acid conversion to 2,3-pentanedione is achieved by condensation, and was first observed in our laboratory at Michigan State University. Carbon dioxide and water are also produced by this pathway. 2,3-Pentanedione is a high-value fine chemical ($70/kg) that is currently produced in limited quantities (4000 kg/yr) through a multistep chemical synthesis or via recovery from dairy waste. Its primary use is as a flavoring ingredient but it has potential for applications as a feedstock (3) , solvent (4) , fuel additive, or photoinitiator for chain reactions (5). There are also major reaction pathways for lactic acid which are undesirable. Formation of acetaldehyde occurs through decarbonylation or decarboxylation of lactic acid. Decarbonylation also forms carbon monoxide and water while decarboxylation forms carbon dioxide and hydrogen. Acetaldehyde is presently produced inexpensively (0.45 $/lb) from petroleum. Reduction of lactic acid produces propanoic acid. Propanoic acid can also be formed by hydrogenation of acrylic acid. Again these methods of production do not hold much promise, as propanoic acid is produced more efficiently 4 and inexpensively from petroleum. Secondary pathways, which in some reactions produced major products, were also found in lactic acid conversion. Those which are known include pathways to acetic acid, acetone, hydroxyacetone, methyl acetate and ethanol. Most lactic acid conversion studies have focused on the dehydration reaction pathway to acrylic acid. Holmen (6) reported conversion over phosphate and sulfate catalysts in 1958. Acrylic acid yields of 68% were achieved over Nazso,‘ at 400°C. Paparizos et al. (7) used ammonium lactate as a feed at 340°C and 4.25 residence time over NHs-treated AlP04 and reported a 61% yield of acrylic acid. Silica-supported NaH2P04 buffered with NaHCOs was used by Sawicki (8) who reported an acrylic acid yield of 58% with a selectivity of 65% at 350°C. Lactic acid reaction studies have produced major products other than acrylic acid. Odell et al. (9) contacted lactic acid with Pt complexes in aqueous solution at ZOO-250°C and found large yields of propanoic acid and 3-hydroxypropanoic acid and only small amounts (<5%) of acrylic acid. Propanoic acid, in absolute yields of 65% at 350°C, was made in another study via lactic acid conversion over a mixed metal oxide catalyst (10). Formation of both cyclic and acyclic lactic acid dimers over silica aerogel at low temperatures was reported by Sholin (11). Formation of lactic acid esters usually occurs during processes which include lactic acid. Concentrating lactic acid aqueous solutions by distillation removes water but at 5 the same time produces lactic acid esters. Lactyllactic acid (CH3CH0HC00CH(CH3) COOH) is the first esterification product but higher linear' esters, that is, trimeric, tetrameric and polymeric lactic acid, are formed as the dehydration proceeds (12). Esterification of lactic acid has also been shown to form cyclic compounds such as glycolide and lactide (12). Pyrolysis of lactic acid and other aliphatic a-hydroxy acids has been reported to produce an aldehyde (or ketone), carbon monoxide, and water (12) . Lactic acid mono-esters also decompose into aldehydes and C0 when heated. The hydroxy esters undergo auto-alcoholysis under suitabLe conditions. For example, when heated in a closed vessel at 250°C for 7 to 8 hours, ethyl lactate yields lactide and ethyl lactyllactate (12). Mok, Antal and Jones (13) published a study of the reaction pathways of lactic acid in supercritical water in 1989. In the study, three primary reaction pathways were described. The first is acid catalyzed decarbonylation which yields acetaldehyde, C0 and water. Second, the decarboxylation pathway yields acetaldehyde, C02 and water. Finally, dehydration produces acrylic acid and water. Acetic acid and acetone are further reaction products of acetaldehyde while hydrogenation of acrylic acid produces propanoic acid and decarboxylation of acrylic acid produces ethene. Effects of solvent concentration, temperature, pressure, and acid catalysts are described in the paper, for each pathway. McCrackin and Lira (14) investigated the conversion of 6 lactic acid in supercritical water in a specially designed reactor. They found that aging their Hastelloy C-276 reactor for approximately 70 hours at reaction conditions increased the yields of acrylic acid by decreasing the alternate pathway conversions. They found a maximum acrylic acid selectivity of 58% at a residence time of 70 seconds and a temperature of 360°C. The maximum acrylic acid selectivity was obtained with a 0.40 M lactic acid solution containing small amounts (< 0.01 M) of phosphate salts. The acrylic acid yields reported in the literature look very promising; if our lactic acid study could improve the results, then our process could be used to produce acrylic acid inexpensively. Also, the discovery of the condensation product, 2,3-pentanedione, has given our research group an added incentive to continue lactic acid studies. An inexpensive method for producing the diketone would be very profitable. The results reported in this thesis describe catalyst and support screening studies directed at achieving high yields and selectivity to 2,3-pentanedione and acrylic acid from lactic acid. CHAPTER 2 EXPERIMENTAL METHODS 2.1 MATERIALS For reaction, the lactic acid feed solution (Purac, 88 wt% in solution) was diluted to 34 wt% prior to being fed to the reactor. High purity (99.99%) helium gas obtained from AGA Gas was used as the carrier. High purity acrylic acid, 2,3-pentanedione, propanoic acid, acetaldehyde, hydroxyacetone, and other chemicals were used as calibration standards. 2.2 CATALYST PREPARATION Various materials were tested as catalyst supports (Table 2.1) and catalysts (Table 2.2). Among the catalysts studied first was biomineral-derived calcium hydroxyapatite, seen as a potentially inexpensive phosphate catalyst. This catalyst was prepared by calcination of bovine teeth in air to remove organic matter, then was crushed to a suitable size before reaction. Other catalysts tested consist mostly of sodium salts which were supported on carbon and/or silica supports. The sodium salt catalysts were generally prepared using the following procedure: First, a quantity of the support to be 7 8 Table — Supports Studied CARBON OTHERS Strem Activated Carbon 1 mm Glass beads Activated Cherry Pits Silica gel Charred Cherry Pits XOA 400 Silica Alltech Carbograph 1 x03 030 Silica Alltech Carbograph 2 XOC 005 Silica Table - Catalysts Studied CATALYST SUPPORTS TESTED ON N83P04 Cherry, Cherry Char, NaOH XOC 005 Silica NaN03 XOC 005 Silica N82HA804. XOC 005 Silica Calo(PO4)6(OH)2 None 9 impregnated was weighed. Then, 0.001 gmol of salt per gram of support was dissolved in a small amount of reverse osmosis watery The support was then added to this solution and.heated on a hot plate until nearly dry. Finally, the support was placed overnight in a vacuum oven which.was heated to 100°C to finish the drying process. Catalyst supports were studied in detail and the performance of each was evaluated for comparison. Carbon supports (see Table 2.1) included activated cherry pits, charred cherry pits, an activated carbon from Strem and two carbons from.Alltech. Silica supports included a silica gel, and three silicas obtained from Anspec. Glass beads (1 mm) were also tested in the reactor. 2 . 3 REACTOR CONFIGURATION The reactor system used for all studies was a vertical, down-flow packed bed reactor equipped with a quartz insert (Figure 2.1). The reactor was chosen to exist in a vertical position because of advantages over a horizontal orientation. The horizontal configuration produced coking in the catalyst bed and.poor'product recovery as a result of incomplete lactic acid vaporization. The body of the reactor consists of a 316 Stainless Steel tube 19.5" long, 1.25" 0D and 0.55" ID. The body is mounted on a wooden stand to make the system portable. A flange closure at the bottom of the reactor is sealed, after catalyst 10 VAPOR-PHASE REACTOR leid . Food ‘ Corn: i .- Fittim , . *______ 3 guitar - ' Mn [:7" Comer M Fr/ ““1“ Clmcll Mr I. Intu- --'— Firehrick b \I‘,‘ U ~ I‘nn-o COS. I“ _U_ \‘-I- . . A- ...,.. I if m: _ luster — — m Lint ' I’d:- 1’de spa-r / p\mm. u. m _ WI m . O a A '. . 9 EQ—’ ' an I E in . tr. . I. Ila-em _P W m‘ .. m . . halve Figure 2.1 .- Reactor system 11 loading, by a spring-loaded metal seal (Helicoflex). This closure facilitates internal access. The reactor system is designed to hold pressure up to 5 MPa at a temperature of 500°C. A quartz liner tube which contains the catalyst is inserted into the reactor from the bottom and sealed to the flange to prevent gas bypass. The quartz-lined interior was used because a metal interior enhanced the undesirable reaction pathways to acetaldehyde and propanoic acid. The liner tube is 19" long x 0.50" OD and contains a coarse quartz frit fused to the tube 9" from one end. The catalyst sits on this frit during reaction. An internal quartz thermocouple well extends from the reactor flange to just below the support frit to measure reaction temperature. A clamshell electric heater controlled by an Omega series CN-2010 programmable temperature controller is used to heat the high-temperature zone of the reactor. The heater is controlled by an external control thermocouple and can achieve a temperature of 600°C. A copper heat sink (6.5" long x 0.5" thick) surrounds the reaction zone to minimize temperature gradients. During a reaction, the catalyst bed temperature is measured by the internal thermocouple. The reactor temperature setpoint. is adjusted. to achieve 'the desired catalyst bed reaction temperature. Flexible heat tapes are used on each end of the reactor. The heat tape upstream of the reactor is used to preheat the lactic acid feed to more readily allow feed vaporization. The downstream heat tape is used mostly to prohibit reaction 12 products from condensing before reaching the collection system. The heat tapes were consistently held at 190°C during system operation. Stainless steel liquid and gas feed tubes (0.062" OD) enter the reactor from the top through a Conax fitting and extend well inside the quartz liner tube. The liquid feed tube extends further into the liner than the helium feed.tube: the liquid feed vapor cannot escape through the top of the liner because the helium stream forces it to flow'down towards the catalyst bed, An Eldex HPLC metering pump is used to pump the liquid feed solution; high purity helium is used to flush the reactor and to dilute the feed during reaction. 2.4 PRODUCT COLLECTION During reaction, reactants and products travel through the catalyst bed, the quartz frit, and then out the bottom of the reactor. The effluent then passes through a 10 ml stainless steel trap placed in an ice bath. This trap collects all condensible products. Noncondensible products flow through a metering valve and a flowmeter and are collected in a gas bag. Liquid and gas products were collected.for a specified.time (20-40 min for liquid.and 10-25 min for gas) during steady state operation of the reactor. Volumes of liquid product collected and gas product collected were measured in order to calculate flow rates and to perform overall mass balance calculations. Liquid product volumes 13 were usually 2-7 ml and gas volumes were usually 200-500 ml. During transient periods of system operation, liquid products were condensed in an 80 ml waste trap and gas products were sent to a fume hood. 2.5 PRODUCT ANALYSIS Condensible products were analyzed with a Varian 3700 Gas Chromatograph with FID detection. A 4% Carbowax 80/100 carbopack B-DA glass column was used in the GC. Liquid product GC preparation included filtering the condensed effluent to remove particulates using disposable syringe filters. Also, the liquid product was mixed with a solution containing 2-propanol as an internal standard and oxalic acid as a column conditioner. One microliter samples were injected directly onto the column while leaving the syringe in the injector for one minute. This assured complete lactic acid vaporization and resulted in reproducible, linear calibration curves for lactic acid. As mentioned earlier, the major Aproducts analyzed were found to be acetaldehyde, 2,3- pentanedione, propanoic acid, and acrylic acid. Reactions involving sodium. salts on silica supports, produced hydroxyacetone as an additional major product. Secondary products include ethanol, acetone, acetic acid, methyl acetate, and several unknowns. These minor products are reported as "Other" in the results. Product yields are calculated from product-to-internal standard peak areas and 14 detector response factors, and are reported as molar percentages Ibased. on 'theoretical lactic tacid. conversion. Figure 2.2 shows a typical Chromatogram. Product identification was conducted by matching of residence time with standards, by gas chromatography/mass spectroscopy, and tnrlfi NMR. A Supelco Spherocarb column in a Varian 3300 Gas Chromatograph was used to analyze gas samples. This instrument uses thermal conductivity for detection. The gas products analyzed were C0, C02 and methane. Yields of CO and C02 are reported on the same basis as liquid products (mole of gas per mole of lactic acid fed). Catalyst dimensions, peak areas from GC runs, liquid and gas product volumes, feed flow rates and concentration are entered into a spreadsheet program designed to calculate residence times, product yields as a percentage of theoretical, selectivities as percentages of products formed, and the overall carbon mass balance for the experiment. 2.6 TYPICAL PROCEDURE Each reaction lexperiment contains some. of the same operating procedures. For instance, in each experiment, catalyst is loaded into the reactor and tested at several increasing reaction temperatures (usually 280, 300, 320 and 350°C). The catalyst is first heated in a helium flow until reaction temperature is reached. Then a relatively high 15 4.39 '.'3'3 Figure 2.2 Typical GC Chromatogram UT ([0 (0:! 16 lactic acid feed flow (0.5 ml/min) is started and run for approximately 15 minutes in order to coat the reactor walls and catalyst bed with lactic feed vapor. Next, helium and lactic feed flows are adjusted to desired setpoints and held there until steady state operation of the system is achieved. When this occurs, product collection is conducted by directing the reactor effluent to the product collection vessel and gas bag for a specified period of time. Usually, this time is dictated by the amount of material which has been fed to the reactor, and should be long enough to collect at least 2.0 ml of liquid product. When collection is complete, the reactor is operated with product flows again directed towards waste streams and the process is then repeated at each temperature to be tested. Most experiments were conducted at either "short" or "long" residence time; a compilation of the two sets of experimental conditions is given in Table 2.3. 1'7 Table 2.3 - Normal Operating Parameters PARAMETER SHORT RESIDENCE (2s) LONG RESIDENCE (6-7s) REACTOR PRESSURE 60 psig 60 psig LIQUID FLOR RATE 0.20 Int/min 0.05 ml/min HELIUM FLOR RATE 40 ml/min 10 ml/min CATALYST 8E0 LENGTH 2-3" I 2-3" CATALYST/SUPPORT 1-3 grams 1-3 grams LIOUID COLLECTION 35 min. (.0 min. LIQUID PRODUCT VOLUME 7 ml 2 ml GAS COLLECTION TIME 700 s 1300 s GAS PRODUCT VOLUME 460 ml 220 ml CHAPTER 3 BIOMINERAL-DERIVED CALCIUM HYDROXYAPATITE 3 . 1 INTRODUCTION When 2,3-pentanedione was found to be a major lactic acid reaction product, an investigation was done to determine the demand for such a compound. We found that the diketone is an expensive specialty compound that is often used as a flavoring agent. A process which would produce the diketone "naturally" could increase its market value. In an attempt to produce the diketone in a natural process, we searched for a catalyst which would be considered "natural", and decided to try biomineral-derived calcium.hydroxyapatite. Bovine teeth were selected as our source of calcium.hydroxyapatite because they are readily available and are an inexpensive source of the hydroxyapatite. The catalytic use of chemically synthesized calcium hydroxyapatite has been documented in the literature. Hydroxyapatite has been prepared by titration of concentrated H3PO4 into saturated Ca(OH)2 by Bett, Christner and Hall (15) . Misono and Hall (16) have shown that hydroxyapatites enhance hydrolysis, dehydration, dehydrogenation, and condensation reactions as well as many others. 18 19 3.2 CALCIUM HYDROXYAPATITE PROPERTIES Biological systems such as teeth and bones are constructed of hydroxyapatite and as such bovine teeth were used in our studies as a source of the catalyst. The ideal unit cell of hydroxyapatite is of the form Ca10(PO4)6(OH)2where the Ca:P ratio is 1.67. In biological systems the ratio is closer to 1.5 which results in the tricalcium phosphate compound (17) . This low ratio is due to C03 substitution, for some hydroxyapatite phosphate groups, in various lattice positions. The lower ratio of calcium to phosphate results in high chemical reactivity. Also, the small crystal size of this hydroxyapatite (220 x 65A) leads to high reactivity (18) . 3.3 CATALYST PREPARATION For our studies, cow's teeth were crushed and then calcined at various temperatures in order to burn off all organic matter; the calcined teeth constituted our catalyst supply. The calcination temperature study consisted of sample calcination at 300, 400, 500, 600, 700 and 800°C before reaction. Catalysts were calcined at 325°C for the particle size study. Calcination was done in a horizontal heated quartz cylinder under a steady air flow. An Omega Temperature Controller ramped the temperature up to calcination point and held it there for four hours before ramp down. The flow of air through the cylinder was maintained at approximately 1 Table 3.1 20 Calcium Hydroxyapatite Properties TEMPERATURE BET SURFACE AVERAGE NEIONT ('C) AREA (ma/9) LOSS (x) 300 5 10x16 140.2 19.48 400 5 10x16 82.5 16.55 500 4 10x16 38.8 16.75 600 4 10x16 28.5 21.37 700 1 10x16 12.2 20.54 II 800 1 10x16 6.2 22.10 “ 325 12 10x16 72.9 19.22 II 325 12 16x30 325 12 soxw 325 12 603000 m 21 L/min in order to carry the organic matter to a collection vessel. Approximately 15 grams were calcined for each run: the catalyst was distributed equally in five ceramic boats which rested in the quartz chamber. Weight loss results during calcination are listed in Table 3.1. 3.4 CATALYST CHARACTERIZATION Total surface area was measured for each catalyst sample by the nitrogen BET method. Surface area results are listed in Table 3.1. As can be seen, there is a twenty-fold difference in surface areas between the sample calcined at 300°C and the one calcined at 800°C. There does not seem to be a trend in surface area with particle size since the highest surface area is found with the intermediate particle size. Mercury porosimetry was performed on each calcium hydroxyapatite sample in order to obtain a pore size distribution. Pore size results are found in Figure 3.1. Complete pore size distributions can be found in the Appendix. Each catalyst sample shows the same general behavior; there are three sizes ranges which contain the majority of pores. Calcination seems to have no affect on the largest two pore sizes. However, the smallest pore size seems to become larger as the calcination temperature is increased, thus explaining the reduction in surface area. An increase in small pores, which is the case at the lower calcination temperatures, 22 85382.65»... E228 to. 832358... 5.6528 .2. gm 20d 09223 . fin 2:9“. as mmaEmmaEE .zo_sx0mn_>_._ . MN_m mmOm m0< (SUOIOIUI) HELLEWVIO ElHOd BOVHHAV 23 usually means more surface area. Relative acidity of the various bovine samples was also studied in order to better understand how acidity affects catalyst performance. The following method was used to calculate the relative acidity of the samples. First, the sample was ground with a mortar and pestle into a powder. A solution containing the powder and KCl was then prepared along with a solution containing KCl only. Equal amounts of the two solutions were then boiled under reflux for two hours, cooled to room temperature, and the pH of each solution was measured. The delta pH, or the difference in pH between the blank solution and the solution containing the sample, was computed. When negative, this number signifies a solution more acidic than the blank, and when positive, less acidic than the blank. The delta pH's of the various samples are listed in figures 3.2 and 3.3. The noticeable trend shows that the samples calcined at the lower temperatures are more acidic than those calcined at the higher temperatures. There is no noticeable trend with particle size. 3.5 EFFECTS OF CALCINATION TEMPERATURE Two separate reaction studies were conducted with biomineral-derived calcium hydroxyapatite. The first study was designed to determine how trends in product yields, selectivity, and activity are affected by calcination temperature. The second study examined various particle sizes 24 6538385»: E2030 0.: to. 2283.5... cos—2:030 .m> In 2.8 . «.n 059". Go mmsimmasmh zo_sx0mn_>: .. In <._.._mo. md Hd 111130 25 ozfingxegz 520.8 2: .2 36 0.25.1 .m> In goo - ad 959". 3625 Ha BEES. oowxow ooxom onxow wwxow mtEm<>xomn>= - In <53 NI Fl Hd vuaa 26 of the calcium hydroxyapatite and how they affect catalyst performance. The catalysts were tested in the reactor at usual operating conditions (see Table 2.3) with a liquid feed rate of approximately 0.05 ml/min and a He flow rate of approximately 10 ml/min. A 34 wt% lactic acid feed concentration was used in each run. Reaction temperatures were usually 280, 300 and 320°C. The results of the calcination temperature study at 300°C and 320°C are shown in Tables 3.2 and 3.3. The absolute product yields and product selectivities (parentheses) are shown for each liquid product. A more complete compilation of reaction results can be found in the Appendix. The results show various trends in selectivities towards the lactic acid reaction pathways based on calcination temperature. For instance, 2,3-pentanedione selectivity increases with increasing calcination temperature. A reaction temperature of 300°C produces higher 2,3-pentanedione selectivities than 320°C. Yields of the diketone seem to go through a minimum at a calcination temperature of 500°C. These yields are relatively low (0.5% - 3.0%) when compared.to some of the other reaction products. Reaction temperature (300°C or 320°C) for these samples does not seem to affect diketone yields. The highest 2,3-pentanedione selectivity for these runs was found to be 25.6% at 300°C from a sample calcined at 700°C. Figures 3.4 to 3.9 show the product yield distributions at each reaction temperature for the various calcination temperature reactions. 27 UGO» «a 850.8 95233852.. E228 05 so. chafing—Eh .m> ago; «Gator... 05.82 - «.6 0.59". 8v mmaimmnsmh zo_5x0m_n_>I - whim; m...=..0mm< 28 88 a .8528 2.588823: 526.8 65 .2 2228.5» .9, «22> .8626 65.83 . ms 2:9... Q mustang—amp zo=oaoo§oo< I 9 I NF o:o_oo:3:oe-m.~. - - 0 - . Ill VF \ .22 33.2 III A e m P m._._._.x0m_o>I .. mo..m.> m._.D-_Omm< (°/.) 0131A ain‘losav 29 88 a .8528 2:36:92: 5328 9: .2 2328.53 .2, .6...» 6:62.. 23.82 . as 2:9“. Q manimmasms zozox0mn_>_._ .. mo..m.> m...:..0mm< (%) 0131A ain‘losav 3O 88 a 856.8 6:38:26»: 526.8 9: to. 228853 .9, 62.; 6:68.. 228.2 . A...” 2.6.“. Q mmnfimmasms zoFozoo§wo< I 9 I ocofiocficoaéfi o - - \ 22 6:32 III QNCOIOQ'OON mt._.x0mo>1 .. m04m_>m._.31_0mm< (°/.) 0131A ain'losav 31 08.. .6 356.8 22323.2: 5228 o... .6. 6.26.8th .9 «22> 8:66... 9282 . as 2:9“. Q mmaimmasm» zo=ox0mn_>_._ - wan—m; m...:..Omm< o n. 0%) 0131A almosav 32 88 a 856.8 2:36.922... 626.8 a... .2 65.6.8.5: .9. «so; .866... 65.82 . as 2:9. Q $3256.25 20.55.. own com ....\..J.\\I m.N .. .. \ xx \ .65o..>i \ m \ \ Eo< Soc—32¢ - 14 I \ x 6626228.. I 9 I md m\ \ oco_oo:5coo-m.~ - - 0 - . + I 22 2.23 III e m... m._._._.x0mn_>I . whim; m...:..0mm< (%) 0131A ain‘losav 33 Table 3.2 - Calcium Hydroxyapatite Results at 300°C CALCINATION TEMP('C) 300 400 500 600 700 800 ACRYLIC ACID 8.47 5.91 3.70 3.14 2.36 1.38 (30.3) (40.5) (54.6) (38.1) (34.4) (21.1) 2,3-PENTANEDIONE 2.38 1.55 0.56 1.10 1.76 1.64 (8.5) (10.6) (8.3) (13.3) (25.6) (25) ACETALDEHYDE 7.03' 4.48 1.26 1.70 1.28 1.44 (25.2) (30.7) (18.6) (20.6) (18.6) (22) PROPANOIC ACID 1.94 0.76 0.19 0.18 0.25 0.74 (6.9) (5.2) (2.8) (2.2) (3.6) (11.3) OTHER 8.13 1.89 1.07 2.13 1.22 1.35 (29.1) (13) (15.8) (25.8) (17.8) (20.6) CARBON MONOXIDE 0.87 2.20 1.02 1.84 1.16 0.73 CARBON oxoxon 2.81 2.18 0.71 2.38 3.27 0.81 CONVERSION 35.81 19.32 19.82 11.33 10.93 9.68 CARBON RECOVERY (x) 98.69 94.85 86.93 , 97.21 96.70 96.52 SURFACE AREA (mzlg) 140.2 82.5 38.8 28.5 12.2 6.2 DELTA pH -2.042 -1.273 -0.854 -0.352 -. 0.263 34 Table 3.3 Calcium Hydroxyapatite Results at 320°C CALCINATION 300* 400 500 600 700 800 TEMPERATURE ('C) ACRYLIC ACID 14.80 17.15 8.62 7.13 6.01 3.71 (31.5) (49.9) (63.3) (43.5) (38.7) (22.8) 2,3-PENTANE0I0NE 0.47(1) 1.73 0.66 1.48 2.73 2.86 (5) (4.8) (9) (17.6) (17.5) ACETALDENYDE 13.88 9.63 2.60 4.34 3.51 4.16 (29.6) (28) (19.1) (26.4) (22.6) (25.5) PROPANOIC ACID 9.01 1.88 0.30 0.40 0.57 2.51 (19.2) (5.5) (2.2) (2.4) (3.7) (15.4) OTNER 8.76 3.97 1.43 3.03 2.72 3.06 (18.7) (11.6) (10.5) (18.5) (17.5) (18.8) CARBON MONDxIDE 4.31. 4.69 1.89 4.45 2.10 2.14 CARBON DIOXIDE 5.95 4.15 3.46 3.87 4.41 4.31 CONVERSION 77.60 43.07 43.52 37.95 35.18 31.98 CARBON RECOVERY 69.75 91.42 70.81 79.04 80.78 84.44 (X) SURFACE AREA 140.2 82.5 38.8 28.5 . 12.2 6.2 (mzlg) DELTA pN -2.042 -1.273 -0.854 -0.352 0.263 Reaction Temperature 350°C 35 Acrylic acid yields and selectivities are higher than those of 2,3-pentanedione for this set of runs. The yields of acrylic acid decrease as calcination temperature increases, while the selectivities go through a maximum at a calcination temperature of 500°CL A reaction ‘temperature of 320°C produces higher yields and selectivities than 300°C. The best yield of acrylic acid was 17.15% at a reaction temperature of 320°C and a calcination temperature of 400°C. The best selectivity towards acrylic acid of 63.3% occurred at 320°C and a calcination temperature of 500°C. Acetaldehyde production is unwanted and therefore low yields and selectivities are desirable. However, in this set of runs acetaldehyde was produced in considerable amounts. Although yields of acetaldehyde were only 1-14%, the selectivities were 18-35% at all reaction and calcination temperatures. Acetaldehyde yields decrease as calcination temperature increases but the reaction conversion also decreases thereby stabilizing the selectivity towards this product. Propanoic acid is produced only in minor quantities. Yields are low, except at high reaction temperatures (350°C), ranging from 0.15% to 1.95% at reaction temperatures of 300°C and 320°C. Selectivities at 300 and 320°C range from 2-15% but most are under 6%. The 800°C calcination temperature gives selectivities of 11.3% and 15.4% at 300°C and 320°C, respectively. The catalyst calcined at 300°C and tested at 36 350°C gave a yield of propanoic acid of 9% and a selectivity of 19%. Other known products found in these reactions are acetic acid and. hydroxyacetone. 'The yields of these products decreases as calcination temperature increases while the selectivities seem to increase somewhat. Yields at 300 and 320°C range from 1-8% and selectivities from 10-26%. Gas product analysis found carbon monoxide and carbon dioxide in varying amounts. No strong trends were found for CO and C02 yields; yields of both gases increase with increasing reaction temperature and range from 0.7-6.0%. The surface areas of these catalysts range from 140.2 m2/g at a calcination temperature of 300°C to 6.2 m2/g at a calcination temperature of 800°C. The lower surface area materials have fewer reaction sites, therefore, one would expect the reaction conversions to be lower for the lower surface area materials. This happens to be the case as conversions do decrease as calcination temperature increases. At the reaction temperature of 300°C, conversions descend from 35.8% to 9.7% as calcination temperature increases to 800°C. At 320°C, conversions decrease from 43.1% to 32.0%. An interesting feature of these samples is the fact that delta pH values increase with reaction temperature. This means that material calcined at the higher temperatures are less acidic than those which were calcined at lower temperatures. Lower acidity of samples calcined at the higher temperatures could help explain the increasing selectivity of 37 the 2,3-pentanedione pathway, which apparently is favored at more basic catalyst conditions. 3.6 PARTICLE SIZE STUDY The second catalytic study conducted.with the biomineral hydroxyapatite was a particle size study. The effect of particle size on catalyst performance was examined in the study, with the goal of finding an optimum particle size. Different particle sizes of a catalyst often can have different physical characteristics, such as pore structure, packing ability, etc., which may affect performance. Three different catalyst mesh sizes were selected for testing: 10 x 16, 16 x 30, and 30 x 60 mesh sizes. The bovine teeth were calcined at 325°C following the procedure given previously. Calcination weight loss data is in Table 3.1. The calcined teeth were then crushed and sized with sieves. The experimental~ runs ‘were jperformed. at normal reaction conditions with a 34 wt% lactic acid feed and liquid and helium flowrates of 0.05 ml/min and 10 ml/min, respectively. The reaction temperatures studied were 280, 300 and 320°C. Key results of the particle size study at 300 and 320°C are found in Table 3.4; a complete compilation of results can be found in the Appendix. Yield and selectivities of 2,3-pentanedione increase as the particle size decreases. This suggests that the smaller particle size favors the diketone production. Figures 3.10, 38 0530322.... :00... or x or 0... .o. 0.20.0920» .2. 00.0; .0300... 05.3.3 - own 059.. Q 0035.005» 20.55... \ .050 I P I 4x Eo< 0.9.08... - Id I 0c>:0p.0.00< I 9 I II 0:o_.00:0.:0d-m.~ - - o - . .22 0.3.0.. III w.._._.xOmD>I .. DIE; thAOmm< 9. ON mm (9.) 0131A aLn'IosaV 39 o~_~aau>xo.u>r_ E2200 :85 an x or 05 .o— Qaeflanh .9. ago; 8:00... 05.9042 - Sun 0.39”. .0. mmaimmasm: 20.55.". I l I l I all I III I I I I I III . I‘ I I lulll III. I I III-I I I ‘l I I IIIIIIIII I I I I I I I I I l I I I I I \I Illl! IIIIIIIIIIIIIIIIIIIIIIII .350 l P l Eo< 0.2.305 . L1 I 03302302. I 9 I 0..o.u0:0...0n-m.~ - . O - . j .22 0.3.2 III m._._.._.x0m_o>I - won—m; m...:..0mm< 6.. m.. cm mm (%) mam aln'losav 4o 02.0%....22... 520.8 :00... 8 x 8 0... .o. 0.20.0..th .9 220... .83... 05.82 . 2.0 050.“. 8. 2:25.52 20.5.3... \ _ .050 I p I or Eo< 0.9.2.0.; - Ifl I III N—. \ 0u>..020.00< I 9 I 0:0.u0cm.c0a.m.~ - . O - . II E. \ .22 23.2. III \ m _. w P mk_._.x0m_n_.>1 .. man—4m; m...:..0mm< (%) mam 3101038V 41 3.11 and 3.12 show the product yield distributions for the 10 x 16, 16 x 30 and 30 x 60 mesh size reaction studies. At a reaction temperature of 300°C and a particle size of 30 x 60 mesh, a 3.15% yield of the diketone is achieved at a selectivity of 18.1%. Although the yield of 2,3-pentanedione is slightly' higher at a reaction ‘temperature of 320°C, selectivity falls off to 8.5% at the 30 x 60 mesh size. Acrylic acid production at all particle sizes is significant in that it is the product found in the greatest abundance in practically every test. As particle size decreases, acrylic yield decreases slightly although selectivity towards this product remains constant. A reaction temperature of 320°C gives the greatest yields of acrylic acid (18-23%). The selectivity towards acrylic is quite high (46- 49%) at a reaction temperature of 320'C. Particle size does not seem. to have a significant affect on acrylic acid production. Acetaldehyde production (yield and selectivity) decreases as the catalyst particle size decreases. This trend coincides with the aformentioned opposite trend of 2,3-pentanedione. These results, coupled with the stability of acrylic acid production, suggest that small catalyst particle sizes give more favorable results. However, even at the smallest particle size (30 x 60 mesh), acetaldehyde formation is appreciable. At a reaction temperature of 300°C, the yield of acetaldehyde is 4.24% which corresponds to a selectivity of 24.3%. At 320'C, acetaldehyde yields are higher but the 42 Table 3.4 - Calcium Hydroxyapatite Particle Size Results REACT ION TEMP 300 320 (°C) PARTICLE 5125 10 x 16 16 x 30 30 x 60 10 x 16 16 x 30 30 x 60 ncavac ACID 8.87 7.16 6.06 23.14 22.15 17.9 (33.2) (34) (34.8) (46.2) (49.1) (46.8) 2,3-PENTANEDIONE 2.90 3.20 3.15 2.05 3.23 3.23 (10.8) (15.2) (18.1) (4.1) (7.2) (8.5) ACETALDEHYDE 9.88 6.92 4.24 17.22 12.44 9.35 (37) (32.9) (24.3) (34.4) (27.6) (24.5) PROPANOIC 4c10 2.59 1.25 1.22 4.11 2.60 2.10 (9.7) (5.9) (7) (8.2) (5.8) (5.5) OTHER 2.49 2.50 2.76 3.52 4.73 5.64 (9.3) (11.9) (15.8) (7) (10.5) (14.8) CARBON nouoxxoe 2.72 10.11 2.67 8.73 7.75 3.39 CARBON DIOXIDE 4.40 9.46 4.81 8.42 8.33 4.67 convens10~ 34.83 23.59 29.77 74.32 51.22 48.95 CARBON RECOVERY 105.56 106.86 99.62 .86.34 103.40 97.68 (3) SURFACE AREA 72.90 84.40 65.06 72.90 84.40 65.06 (112/0) DELTA pH -1.26 -1.26 -2.10 -1.26 -1.26 -2.10 43 selectivity towards this product is relatively constant. Yield of propanoic acid at each reaction temperature decreases as the catalyst size decreases, which also supports the conclusion that the smaller mesh size is most desirable. Selectivities of propanoic acid vary from 5 to 10% based on reaction conditions but they do not seem to follow a trend with catalyst size. The 320°C reaction temperature gives yields which are approximately twice those of the 300’C reaction temperature while selectivities at each reaction temperature are relatively constant. Yields of the other reaction products do not follow any strong trends with particle size, but selectivities of the other products seem to increase as the catalyst particle size decreases. These minor products consist primarily of ethanol, acetic acid, and hydroxyacetone. Reaction temperature has little affect, if any, on the selectivity of these products. The greatest combined yields and selectivities are found with the smallest particle size and are approximately 6% and 15%, respectively. Gas product analysis shows formation of only carbon monoxide and carbon dioxide from reaction. The ratio, 00:002, in most cases is close to unity and there seems to be no particle size based trend in the ratio. Gas yields range from 2-10%. Lactic acid conversion decreases with particle size with one exception at a reaction temperature of 300’C and a particle size of 16 x 30 mesh. Conversion, in each test, 44 increases with reaction temperature which is a very normal result. The highest conversion of 74.3% is found at a reaction temperature of 320°C and a particle size of 10 x 16 mesh. Reaction temperatures higher than 320‘C were not tested in this study. The lowest conversion of 17.65% was found at a reaction temperature of 280°C and a 30 x 60 mesh particle size. The mass balances for the particle size study were excellent in relative terms. Carbon recoveries ranged from 86 to 106% with only one figure greater than 10% loss. CHAPTER 4 CARBON SUPPORTS An attempt was made to identify a carbon support which would produce very little acetaldehyde and propanoic acid when lactic acid was passed over it. If such a carbon was found, we planned to impregnate it with catalyst and react lactic over the supported.catalyst. Five carbon supports were chosen for study; they are shown in Table 4.1. The Table also shows the total surface areas of the carbons as well as other physical properties. As can be seen, a huge contrast in surface area exists between the carbons, from 1600 mfi/g to 5 mz/g. Aside from sizing the carbon particles there was little support preparation. The Strem activated carbon was ground to 10 x 16 mesh for reaction and calcined at 800°C for one hour. The particle sizes for the other carbons are given in Table 4.1. All reactions were completed following the long residence time reaction parameters given in Table 2.3. Complete carbon support results can be found in the Appendix. 4.1 STRBM ACTIVATED CARBON The first carbon support studied was Strem activated carbon. Figure 4.1 shows the product yields versus reaction temperature for Strem activated carbon. The product 45 46 588 00.022 52.0 6... .6. 0.20.0053 .9. 020... 8:3... 05.82 - F... 0.30.“. .0. 0032006202 22520.. own cum com com _ _ Fm ...... >1--I.-I--I--I.>I:I:I:I: ..... I\ \ 11-11fi/ OF ....... «.1 I / / I 2 7 m. m \ /. \ z /. o F \\ -/ PO" m //l \\ // .I— // \x / mN 3 /// \\ // m ,0 // O” m . 9 .7” .050 I». I // mm 01 6.8226288... I 9 I / o_o< 0.2.08... - La. I 40¢ ,mv 20mm<0 omh<>_._.0< Eur—kw - 04m; thAOmm< 47 distribution is dominated by acetaldehyde and propanoic acid. Yields of 2,3-pentanedione and acrylic acid were found to be less than 1% at all temperatures tested. The other liquid reaction products, ethanol, acetic acid and hydroxyacetone, were also minor, and combined, accounted for combined yields of only 5-10%. Gas product analysis showed that production of C0 and C02 was prominent, with a C0:C02 yield ratio near unity or slightly greater than unity in all cases. The activity' of the Strem carbon. was high at all temperatures. At 280°C, the conversion was 82.4%: it increased to 99.9% at 375'C. The large surface area of this carbon may have contributed to its high activity. High surface area materials usually have more reaction sites than lower surface area materials. Even more important in this case, however, the microporosity of the carbon may cause the condensation and cracking of lactic acid to acetaldehyde. The carbon error at 280'C was only 2.3% for the Strem carbon, which means that 97.7% of the original carbon in the lactic acid feed was recovered. The error became much larger at higher temperatures. At 300, 320 and 350’C the carbon recoveries were 63.2, 69.9 and 67.8%, respectively. The low recoveries indicate that less carbon was recovered than that which was fed through the reactor, suggesting that cracking is important. The most favorable results are found at 300°C but this is also where the largest mass balance error (63.2% carbon recovery) occurs. Here only 64% of the carbon fed during reaction is recovered. The result of this large error 423 Table 4.1 - Carbon Reaction Parameters SUBSTRATE PARTICLE SURFACE REACTION SAMPLE $122 (mesh) AREA (09/0) TEMPS. ('C) 5125 (g) STREH ACTIVATED 10 x 16 1600# 280, 300, 320, 2.1 CARBON 350, 375 STREH H/NA3P04 10 x 16 1600# 230, 250, 280, 1.8 300, 320, 350 ACTIVATED 10 x 30 10001! 280, 300, 320 2.1 CHERRY CARBQI CHARRED Cl-IERRY 10 x 16 40* 280, 300, 320, 2.3 CARBON 350 CHARRED CHERRY 10 x 16 40* 280, 300, 320, 1.9 u/NA3PO4 ‘ 350 CARBOGRAPH 1 60 x 100 80* 280, 300, 320, 2.0 350 CARBOGRAPII 2 60 x 100 10 280, 300, 320, 3.1 350 = I! - Measured by 002 adsorption at 298K, 26.2 A/mlecule 002 * - N2 BET area 49 is the appearance of lower yields. Even at this temperature, however, product selectivity greatly favors acetaldehyde and propanoic acid (see Figure 4.2). Overall, the Strem carbon did not show much promise as a support. It was very active, but the high activity was directed to the wrong reaction products. Acetaldehyde and propanoic acid yields were too high and selectivity towards the desired products was practically non-existant. The Strem carbon was impregnated with Na3P04 in order to determine if the salt could affect the poor support performance in a positive manner. Impregnation with the trisodium phosphate consisted of placing 0.0025 gmol of Na3P04’12H20 per gram of support on the support. The long residence time reaction parameters were utilized for the experimental run. Figure 4.3 shows the yield distribution for the Na3P04/Strem carbon catalyst. Again, acetaldehyde and propanoic acid yields were very high and desired product yields were low. Gas analysis showed that the CO:C02 yield ratio was approximately 0.5 throughout the experimental run. This is different from the ratio of about 1.0 found with the support alone. As this was one of the few differences in the Strem carbon versus Na3P0‘/Strem carbon results, we concluded that Na3P04 did not seem to affect the reaction performance of the Strem carbon in a positive manner. 50 Goon mka=o< Spam 05 .0. «02.3.8.8 «0300...... - N2 0.59". 3.0.00. 260 26:06.28 3.0.0... 032020.02. 1. ..... . 36...... .050 .2... : 0-0.0 .230. .260 2.22 952.0010 0... >._._>_._.Om._mm 51 c0900 E25 05 :0 000902 .2 Qaaflanoh 20> 00.0; 8300.0 05.00.“: I m6 0.590 .0. 005200825 2920200 000 can com 000 _ _ m . o F - - mp .050 \ \ \ \ o.0< 0.2.0020 I I I I- \ ON 6.620283... ...... \ \ \ \ III/III \\\-\ 00 on 20mm<0 Sum—hm 20 00090.2 (9.) a1aIA aln'losav 52 4.2 CHERRY-DERIVED CARBON The next carbon studied was an activated cherry pit carbon with a surface area of approximately 1000 nfi/g. The activated carbon was prepared by steam activation of charred cherry pits at 800'C for two hours as part of another ongoing research project. ‘We expected high conversions as seen in the high surface area Strem carbon, and observed conversions averaging 85% over all temperatures. Figure 4.4 shows the product yields at the temperatures of reaction. Acetaldehyde dominates the product mixture, (23- 35% yield), with propanoic acid yield ranging from 6-8%. Acrylic acid and 2,3-pentanedione yields were less than 1% at all temperatures. Acetic acid constituted the largest portion of the minor product yields (1.6-2.3%). Selectivity to acetaldehyde was even greater than that found in the Strem carbon. The gas analysis showed a co:co, yield ratio which decreased from 2.5 at 280'C to 1.5 at 320'C. Carbon monoxide yields were large in comparison to previousvalues (see Tables 4.2 and 4.3). Cherry carbon mass balances were not very good. At 280'0, 82.7% of the carbon was recovered and at 300 and 320°C this figure was approximately 70%. 53 56.00 3.2.0 00.022 2.. .6. 820.0050» .2 8.0... .8020 65.82 - e... 050.. own .0. 0022000202 zoFo<00 can emu _ o ......... m 3 .050 I b. l m.. u.0< 0.o..00o.0 - I4. I 002020.82 I 9 I cm .1 .. ,,,,,,,, I I 47 I I 00 III/I on L4mm (1%) 013111 almosav 20mm<0 >mmmIU Dm._.<>_._.0< . DIE; m..3..0mm< 54 4.3 CHARRED CHERRY PIT8 To avoid the possible deleterious effects of microporosity in activated carbons, low surface area (40 mz/g) charred cherry pits were studied. 'These were expected to show less activity than the higher surface area materials. Reaction conditions are shown in Table 4.1. Figure 4.5 shows the liquid product yields from lactic acid reaction over the charred cherry pits. Acetaldehyde production is suppressed when compared with previous carbons; yields are consistently under 10% at all reaction temperatures. At 320'C the acetaldehyde yield is only 5%; this yield increases to 9% at 350‘C. The yield of propanoic acid is at 4% at 300°C but approaches 15% at 350'C. Propanoic acid is the favored liquid product at the higher reaction temperatures. Yields of 2,3-pentanedione are modest but much greater than with any other carbons. The diketone yield peaks at 8% (300'C - 320'C) and falls off to 3% at 350°C. Acrylic acid yield is also small but it does reach 6% at 320‘C. The other liquid products of reaction consist mainly of hydroxyacetone and acetic acid. Gas analysis showed little CO production and a great deal of 002 production. The 00:002 yield ratio ranges from 1:3 to 1:20 at different reaction temperatures. This could be in some way a result of the low surface area of this material. Conversions after accounting for the mass balance errors 55 2.0 52.0 02.2.0 9.. .6. 05.0.0050» .2, 0.20... 638.0 05.82 - m... 050.0 .0. 0052000202 29204.00 cmm own com .x. .0...oI>.I . A p.0< 0.9.0020 - La. I \ . 030020.004. I 9 I -I. 0:o.00:0.:00-m.~ - - 0 - . .22 25.2 III. m..._0 >mmm10 ommmdfo - 04w; m...:..0mm< 3. or (%) 013111 5110103811 56 are 23, 34, 55 and 64% at 280, 300, 320 and 350'C, respectively. The conversions at low temperatures are less than those of previous carbons. The mass balances again are not very good, ranging from 95.1% carbon recovery to 66.6% recovery at 280’C. At 280°C, the 66.7% carbon recovered led to a huge conversion error. The calculated conversion was 58.3% but this includes the 33.3% of carbon that was not collected. The promising product yields and suppressed acetaldehyde formation led us to impregnate the charred cherry pit support with Naspo, to determine if reaction performance could be improved. The previously mentioned impregnation method was used except the amount of salt placed on the surface was 0.001 gmol salt per gram of support. Figure 4.6 shows the product yield results for the Na3PO¢charred cherry pit catalyst. The most noticeable difference between the catalyst and the support alone is in the acrylic acid yields. Over the support alone, acrylic acid yield barely reached 6%, but with trisodium phosphate added, the yield of acrylic approached 13% at 320°C. At 300‘C, the acrylic acid yield was almost 7% where before it was only 3%. The yield of 2,3-pentanedione did not change much, and the same plateau behavior (9% at 320’C) was seen in this catalyst. Propanoic acid yield was somewhat suppressed by the introduction of trisodium phosphate. With the support alone, at 350‘C, the propanoic yield approached 15%. With the catalyst added, this yield was 11%. Production of 57 2... .520 8:20 co eoanaz 3. 2388.5» .2 «so... 8285 23.82 . 3 2:0... .0. $325625 zoF0mmmIO ZO «On—m oz - DIE; m...=...0mm< 58 acetaldehyde was for the most part constant and remained low except at the highest temperature. The ratio of CO to C02 yields was again much less than unity and ranged from 1:6 to 1:13. C02 yields were generally higher than those found when testing the support alone. Conversions accounting for mass balance errors were 25, 49, 64 and 67% at 280, 300, 320 and 350'C, respectively. These conversions are slightly higher than those calculated from the charred cherry pits only. The mass balances are better than those found using the support alone, ranging from 85.4% carbon recovery to 74.7% recovery. Over 80% of the carbon was recovered at every temperature except 350°C. 4.5 CARBOGRAPH CARBONS Two carbon samples were purchased from Alltech, Carbograph 1 and Carbograph 2, for lactic acid reaction. The first of these, Carbograph 1, was determined to have a surface area of 80 nfi/g and a 60 x 80 mesh particle size. Particles were spherical and black. The experimental run was conducted using the parameters listed in Table 4.1. Figure 4.7 shows the liquid product yields for all reaction temperatures. Acetaldehyde yields dwarf all other liquid. products, even ‘though at lower ‘temperatures, the support activity is quite low. At 280‘C, the acetaldehyde yield is less than 4%, but it reaches its high (18%) at 350'C. Propanoic acid yield ranged from 1% at 280'C to 8% at 350'C. 59 p £363.00 .2 0.220053 .m> no.0; .0:on 23.00.: - he 2:2... .0. $3256.25 zoF0.I 3 \\\ 0.0.3.2512... - I<.I mp \ \ oo>zoo§oo< l 9 I m-. ON F Ia 00.0; .0255 2:323 . ad 959". .0. 05536.25 20:03.... own can can ch ' ‘ I | ‘ - ~ \ .050 l b. I \ 20< 0.2.2.2.". - Ii. I \ 82.02382 I o I N Im._._>_._.Um._mm 64 formation of acetaldehyde and propanoic acid. The charred cherry pits did a far superior job than any of the other carbon supports as far as product selectivity is concerned. However, there was some production of acetaldehyde and propanoic acid and at a reaction temperature of 350°C, they were by far the most selectively produced liquid products. All carbon supports *were characterized. by' an increasing tendency towards acetaldehyde production at high temperatures. Tables 4.2 and 4.3 show the reaction results for all carbon supports at 300 and 320°C, respectively. The reaction yields and selectivities to liquid products (parentheses) can be compared easily. Conversions can be seen to increase with temperature and with support surface areas. Tables 4.2 and 4.3 also show'the mass balance results for the supports at the listed reaction conditions. Overall, mass balances were not very good but there were no huge material losses. Condensation.and cracking of the lactic acid.over the carbons seems to have been important due to support microporostiy. This cracking of the lactic acid probably led to the poor mass balances. The two Carbographs had the best mass balances probably due to a less microporous structure. 65 Table 4.2 - Carbon Support Results for 300°C SUBSTRATE STREH CHERRY CHERRY CARBOGRAPH 1 CARBOGRAPH 2 CARBON CHAR ACRYLIC ACID 0.04 0.64 3.10 0.34 0.96 (2.4) (1.0) (13.1) (3.6) (17.1) 2,3-PENTANEDIONE 0.61 0.54 7.99 0.12 0.07 (1.7) (1.5) (33.0) (1.3) (1.3) ACETALDEHYDE 17.37 .25.15 4.19 6.25 2.04 (40.0) (69.4) (17.7) (66.6) (50.5) PROPANOIC ACID 10.60 6.20 4.64 2.19 1.40 (29.0) (17.1) (19.6) (23.4) (24.0) ACETOL 0.0 0.32 2.53 0.0 0.0 (.9) (10.7) 01052 6.20 3.30 1.20 0.40 0.36 (17.4) (9.3) (5.1) (5.1) (6.4) co 27.43 45.06 1.01 10.60 3.72 c02 20.65 16.97 19.54 6.90 3.05 couvensnou (x) 05.06 06.26 30.51 10.00 ‘23.73 04000» necoveav 63.25 60.02 95.09 107.76 06.35 (X) 66 Table 4.3 — Carbon Support Results for 320°C SUBSTRATE STREH CHERRY CHARRED CARBOGRAPH 1 CARBOGRAPH 2 CARBON CHERRY ncnvac 4010 0.40 0.03 6.62 0.74 0.49 (.7) (2.1) (10.9) (4.1) (4.3) 2,3-PENTANEDIONE 0.27 0.55 7.76 0.17 0.17 (.5) (1.4) (22.2) (.9) (1.5) ACETALOEHYDE 30.93 23.49 5.02 12.62 5.59 (57.1) (60.5) (14.3) (60.0) (40.0) PROPANOIC ACID 14.19 8.62 9.30 4.54 3.10 (26.2) (22.2) (26.6) (30.3) (27.0) ACETOL 0.0 0.02 5.03 0.0 1.31 (2.1) (14.4) (11.4) 01022 0.34 4.50 1.29 0.27 0.00 (15.4) (11.6) (3.7) (1.5) (7.0) co 29.33 27.66 4.04 14.70 5.96 c02 24.37 19.71 32.75 16.00 9.63 CONVERSION (x) 94.67 04.00 75.46 45.51 41.00 CARBON RECOVERY 69.00 69.55 77.14 91.74 86.80 (x) CHAPTER 5 SILICA SUPPORTS In the course of our catalyst/support search, various silica containing supports were studied. These supports are listed in Table 5.1 along with some physical properties including reaction particle size and surface area. A large surface area range was chosen; therefore, we expected widely varying reaction activity results. All supports were run using the long residence time operating parameters. 5.1 GLASS BEADS Glass beads (1 mm diameter) were the first support to be studied. The very low (< 1 mz/g) surface area of the beads seemed to suggest that there would be little activity as lactic acid was passed over them. Figure 5.1 shows the absolute yield data for the liquid products obtained from the glass beads experimental run. There was not much reaction, even at the highest reaction temperature, 320’C. All major reaction products (acrylic acid, 2,3-pentanedione, acetaldehyde, and propanoic acid) were produced in small quantities. All yields of these products are between 0.5 - 2.5% at all reaction temperatures. Although product yields are very small, there is a noticeable trend of product yields increasing with reaction temperature. Selectivity to acrylic 67 68 «.680 86.0 En: 8. 2282.53 .2, 60.6... .2620 05.82 - 3. 2:0... .0. 0.0320020» 20:22 ONm com “3. c m. P .050 I D I 22 0.2.0026 - 1.1 I ou>=02200< I 9 I N ocofiwcmucooéfi - - 0 - - 0.2 6.....2 III m.N ma «22> «0300.5 05.022 I Nd 0.59“. .0. 22556.23 zoF0zo_0_200< I 91 H\ om om ._m0 <0_.=m I 04m; NPDJOmm< (9.) 0131/1 almosav 72 acrylic acid and 2,3-pentanedione yields are also consistently less than 5%. Carbon monoxide production is far greater than that of carbon dioxide at all reaction temperatures: CO:C02 yield ratios range from 4:1 at 350°C to 17:1 at 300°C. Yields of both gas products increase with temperature. Conversions corrected for carbon error were 22, 26, 36 and 63% at 280, 300, 320, and 350°C, respectively. Mass balances for this study were not bad as over 75% of the carbon initially passed over the support was recovered at each temperature. Carbon errors were again lowest at the lower reaction temperatures with recoveries of 88 and 94% at 280 and 300'C. Table 5.2 - Calcination Temperature vs. Surface Area CALCIIAT [GI TEMPERATURE SAMPLE BE I 0111’ (9) SURFACE AREA (1112/9) ('C) 110011 TEMPERATURE 0.33 301 340 0 . 12 274 560 0 .31 308 900 0 . 21 232 The silica gel was calcined in a Thermolyne 1300 furnace at several temperatures and nitrogen BET was performed on each 73 sample for surface area determination. We were attempting to decrease the materials microporosity by calcination in hopes that it would decrease acetaldehyde production. Table 5.2 shows the surface area results and one can see that there is little difference in surface areas as a function of calcination temperature for the silica gel. However, the surface area is slightly lower for the material calcined at 900°CL We expected to see decreased activity for this support and possibly some suppression of the acetaldehyde reaction pathway. Figure 5.3 shows the liquid product yield results for'the silica gel material calcined at 900°C. Reaction parameters for this study are listed in, Table 5.1. Acetaldehyde production, again, is far greater than any other liquid product. Acetaldehyde yield reaches its peak of 38% at 320’C. Propanoic acid only reaches a yield of 8% at 350°C. Acrylic acid and 2,3-pentanedione yields are low at each temperature and other liquid products are present in very small quantities. The gas product yields are similar to those seen in the uncalcined silica gel. Carbon monoxide production is greater than.that of carbon dioxide at all reaction‘temperatures. The CO:C02 ratio ranges from approximately 7:1 at 300'C to 2:1 at 350'C. As seen before, CO2 production becomes closer to CO production at higher temperatures. Lactic acid conversions are 21, 30, 53 and 57% at 280, 300, 320, and 350’C, respectively, which is similar to the 74 .60 8...0 820.00 .6. 658.8.th .0.. 8.6.» .83... 65.82 I 0.... 2:0... .0. 0035.323 295%.... 08 on» 08 SN _ -I-I.I.._.II.I.II...I....IS -\I41-II-H.I.\-I\ \ IIII.\.\..» \ m N: 2. mp .25IPI \4 o.0<0.ocmoo.n_ 14. I \ \ \ ON 0/ wu>nm£muwo< | 9 l \ \ \ /// \uQ\ mN )// (\I\ on // \\\ mm ,9 av .50 4.0.1.5 DwZ_0._<0 I DIE; Frau—Own... (%) malA aln'losav 75 uncalcined material. Mass balances are poor for this particular study: only at 320°C was more than 75% of the original carbon recovered. The largest carbon error occurred at 280°C where only 66% of the carbon in the lactic acid feed was recovered. 5.3 SPHEROSIL SUPPORTS The first of the three Spherosil silica supports to be studied was the high surface area (400 nfi/g) XOA 400 sample. Because of its high surface area, it was expected that this support would show greater activity than the others. The Spherosil samples were tested using the parameters listed in Table 5.1. All the Spherosil samples were smaller particles (80 x 100 mesh) than any of the other silica supports. Figure 5.4 shows the liquid product yield results for the XOA 400 silica support. Acetaldehyde production dwarfs all other liquid products at each reaction temperature. There is, however, a peculiar trend as the acetaldehyde yield decreases at each temperature. Acetaldehyde yield reaches its peak of 67% at 280'C and decreases to 34% at 350‘C. Propanoic acid yield begins very slowly (0.5% at 280'C) but reaches 7% at 350'C. Acrylic acid and 2,3-pentanedione yields remain less than 1% at all reaction temperatures. Other liquid products are only present in extremely small quantities. Gas analysis shows a great deal of carbon monoxide production which decreases with increasing reaction 76 850 8e (Ox 05 .0. ceauflwaEuh .m> ago; Lbs—00...". 05.8n< I Rm 0.50.... .0. #525025 2955... own an com omN . . ........ O I ............. . . R I I or on 0 I .26 I >. I on x x / 6.62.6208... I 9 I / / I O? 7,) cm 1., I I / III/911111 00 Jon :op_900< I 9 I On aI mm I 00 4035 one mOx I DIE; thAOmm< (%) (naIA almosav 79 products are present only in very small quantities. Gas product analysis once again shows greater carbon monoxide production than carbon dioxide. Production of both gas products is lower than for the XOA 400 support. The CO:C02 yield ratio ranges from 6:1 at 280'C to 1.6:1 at 350°C. This again shows C02 production catching the CO production at higher temperatures although yields of both gas products increase with reaction temperature. Lactic acid conversions are 16, 26, 37, and 65% at 280, 300, 320 and 350°C, and are much more normal than those found for the XOA 400 support. Mass balances were better with recoveries exceeding 75% at all temperatures except 320'C where only 73% of the carbon was recovered. There still is present a loss of carbon which implies that condensation and cracking may still be important here. The last Spherosil support to be studied was the XOC 005 sample which has the lowest surface area (14 mz/g) of the three samples. The support was tested using the parameters listed in Table 5.1. Again, it was predicted that the lower surface area material would show less activity and would suppress acetaldehyde production. Figure 5.6 shows the liquid product yields for the XOC 005 support. Acetaldehyde yield is again the most dominant product although it is less abundant than in the previous two studies. Acetaldehyde yield starts at 4.7% at 280‘C and only reaches a high of 13.7% at 350'C. The suppressed acetaldehyde yield is accompanied by suppressed yields of all other liquid 8O 02:0 moo 00x 05 .0. 0.350550... .m> ”22> 8:69.... 05.02? I 9m 0.30.“. .0. 0035.00.23 zoFo.ll|. OF \M \\ \ 0.2.0.35 - I4. I h/I \\\ ou>nmE0~00< I9 III] N_. +II 0.. <0_4.m mco 00x I DIE; m...:..0mm< 81 products including propanoic acid, which ranges from a yield of 0.6% at 280’C to 5.8% at 350°C. Acrylic acid and 2,3- pentanedione yields are less than 2% at all reaction temperatures. Other liquid products are present in extremely small quantities. Gas product analysis shows the same general trend of greater carbon monoxide production than carbon dioxide with Coszroduction increasing faster with reaction temperature. CO:COz ratios range from 3:1 at 300°C to slightly less than unity at 350'C. Yields of both gases are lower than those of the previous two Spherosil samples. Lactic acid conversions were 12, 14, 20 and 40% at 280, 300, 320, and 350'C and are lower than the other two Spherosil supports, as expected. Mass balances are good at the lower reaction temperatures but are very poor at the higher temperatures. Carbon recoveries range from 108% at 280°C to only 53% at 350°C. Table 5.3 (shows summarized results for the three Spherosil silicas at 300 and 320°C. The absolute product yields are shown along with the product selectivities in parentheses. The XOC 005 support shows the lowest acetaldehyde production and the best results even though the product distribution still greatly favors acetaldehyde on a relative basis. It is the suppression of acetaldehyde yield that is most significant, however, and this feature is the cause behind more studies being done with this support. 82 Table 5.3 - Spherosil Silica Results at 300 and 320°C TEMPERATURE ('0) 300 320 SUBSTRATE x0A 400 x00 030 xoc 005 x0A 400 x00 030 xoc 005 ACRYLIC ACID 0.33 1.04 0.27 0.80 2.73 0.79 (0.5) (6) (4.9) (1.3) (0.4) (5.6) 2,3-PENTANEDIONE 0.26 0.04 0.22 0.31 1.93 0.60 (0.4) (4.9) (4) (0.5) (5.9) (4.0) ACETALDEHYDE 61.12 13.36 4.56 54.5 22.95 10.33 (93.0) (77.4) (02.9) (09.1) (70.5) (72.6) PROPANOIC AcIo 1.03 1.71 0.45 2.74 4.25 1.77 (1.6) (9.9) (0.2) (4.5) (13.1) (12.4) OTHER 1.39 0.31 0 2.27 0.60 0.65 (2.1) (1.0) (3.7) (2.1) (4.6) co 74.6 15.7 3.5 51.9 10.0 7.9 C02 7.1 ‘ 3.2 0.9 14.1 5.0 4.0 CONVERSION (X) 00.23 37.61 10.91 96.00 63.50 52.46 CARBON RECOVERY 91.69 00.43 94.75 _ 71.06 73.30 67.94 (X) CHAPTER 6 CATALYST SURVEY The Spherosil XOC 005 silica support was used in a catalyst survey which was intended to produce a superior catalyst/support combination. It was decided that the catalyst search would employ the short residence time operating parameters. The catalysts which were chosen are sodium salts and are listed along with their physical properties in Table 6.1. It was assumed that the XOC 005 support surface area of 14 m2/g remained approximately constant after impregnation with the various salts. Preparation of the catalysts was basically identical in all cases. A loading of 0.001 mol catalyst per gram of support was chosen for each study and impregnation was carried out using the methods described earlier (Chapter 4). Figures 6.1 - 6.5 show the liquid product yields for the XOC 005 support and each catalyst studied. The support alone showed very little activity'at.the lower'temperatures and.even at 350'C, the acetaldehyde yield is only 9% with all other liquid products combining for a 2.3% yield. Acrylic acid, 2,3-pentanedione and propanoic acid yields are less than 1% at each temperature. Lactic acid conversions are 4, 6, 10 and 20% at 280, 300, 320 and 350'C when the carbon errors are accounted for and mass balances are fair with carbon recoveries of 85, 102, 105 and.82%. Gas product formation is 83 84 8....I. 08 09. o... .0. 6.20.853 .0., 00.0; 8:06... 05.82 - .0 0.00.". .0. 0052000200 29020.. omm on oom omN _ . MD b. ..... I IIIIIIII \ II IVIVINII ........... _. t I \\\ N \.I m \ x. v \ I m x \\ _ .050I>.I_ o _\ 00300.58... I 9 I \I . I h x \ m x I m <0...=m moo 00x I 04m; m...:..0mm< (9.) CI'IEIIA almosav 85 8...... 08 09. =0 .602 .0. 0.30.002...» .2, 00.0... 6:020 80.82 . «.0 0.00.0 .0. 002500020» zo..6<0.0 +\-\ .050IDII o.0< 0.9.035 . I4. I (9.) (1131/1 Elln'IOSGV .202 IVTI oF 00>:00_0.00< I .9 I 0:o.00..0...0...m.w - I 0 I - N .- 0.2 6.....2 III . E <0_I=m moo 00x 20 1002 I o..m.> m...:...0mm< 86 00:.0 moo 00x 0.... :0 005002 .0. 0.30.0050... .0> 0.0.0; 83.00... 05.00o< I 0.0 0.39“. .0. 000200025 22.84.00 \ \ II \\ II \I\ .05OI>.I o.0<0.o..0ao51<.l S (9.) 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O._. >._._>_._.Um._mw 93 catalysts as far as 2,3-pentanedione production is concerned. Also, acetaldehyde production is suppressed at the lower temperatures. Yield of 2,3-pentanedione reaches a peak of 23% at 300°C while acetaldehyde yield is less than 3%. Figure 6.8 shows the selectivity to products at 300’C. Conversions were fairly high for this study (20 - 71%). Although the results for the Na2HAsO4 were very good, the commercial potential for arsenate catalysts is not good as arsenic is a very dangerous substance. 94 Doom mm3h._._>_._.Om.._mm p k 95 Table 6.2 - Catalyst Survey Results at 280°C SUBSTRATE SUPPORT NaOH Na3PO4 NaNO3 Na2HAsO4 ACRYLIC ACID 0.22 0.53 1.41 1.61 2.02 (13.5) (15.1) (17.2) (17.1) (14.3) 2,3-PENTANEDIONE 0.03 1.31 4.02 5.15 9.24 (2) (36.9) (49.3) (54.9) (65.2) ACETALDEHYDE 0.59 0.58 1.1 0.91 1.44 (35.5) (16.3) (13.5) (9.7) (10.1) PROPANOIC ACID 0.38 0.6 0.87 0.63 0.83 (22.7) (17) (10.7) (6.7) (5.8) HYDROXYACE TONE 0 0 0 . 2 O . 56 0 (2.4) (5.9) OTHER 0.44 0.52 0.57 0.54 0.65 (26.3) (14.8) (6.9) (5.7) (4.6) co 0.52 ‘ 0.55 0.88 0.96 1.57 c02 0.46 1.2 3.48 4.32 11.27 CONVERSION ‘ (X) 18.84 14.9 7.65 17.22 41.08 CARBON RECOVERY 85.21 91.51 104.98 96.19 78.66 (x) 965 Table 6.3 - Catalyst Survey Results at 300°C SUBSTRATE SUPPORT NaOH Na3P04 NaNO3 NazHAsO4 ACRYLIC A010 0.21 1.49 3.7 5.31 6.01 (10.1) (21.6) (21.3) (22.1) (17.4) 2,3-PENTANEOIONE 0.14 3.45 7.16 10.91 23.34 (6.6) (50) (41.1) (45.4) (67.5) ACETALDEHYDE 0.96 1.34 2.96 3.77 2.64 (46) (16.5) (17) (15.7) (7.6) PROPAHOIC A010 0.38 0.83 1.26 0.8 1.14 (18.4) (12) (7.2) (3.3) (3.3) HYDROXYACETONE 0 0 1.79 2.93 0.95 (10.3) (12.2) (2.8) OTHER 0.39 0 0.54 0.32 0.49 (18.8) (3.1) (1.3) (1.4) co 1.28 1.05 1.41 1.81 1.76 002 0.68 _3.68 7.63 12.24 16.76 CONVERSION (x) 4.06 21.05 47.71 37.94 44.17 CARBON RECOVERY 102.68 89.95 75.63 93.57 94.88 (X) 9'7 Table 6.4 - Catalyst Survey Results at 320°C SUBSTRATE SUPPORT NaOH Na3P04 NaNOg NaZHASO4 ACRYLIC ACIO 0.29 3.97 8.68 13.49 12.92 (7.6) (22.9) (26.6) (35.6) (27.2) 2,3-PENTANEDIONE 0.20 6.79 10.90 13.44 8.07 (5.2) (39.1) (33.3) (35.5) (17) ACETALOEHYOE 2.96 3.05 5.13 2.76 1.10 (78.3) (17.6) (15.7) (7.3) (2.3) PROPANOIC ACID 0.34 1.30 2.38 0.92 6.81 (8.9) (7.5) (7.3) (2.4) (14.4) HYDROXYACETONE 0 1.76 5.18 6.87 0.5 (10.1) (15.8) (18.1) (1.1) OTHER 0 0.49 0.44 0.38 0.5 (2.8) (1.3) (1.1) (1.1) CO 4.72 1.51 3.00 2.30 2.52 C02 1.31 8.40 '15.59 17.76 25.65 CONVERSION (x) 5.15 23.40 66.48. 63.94 77.04 CARBON RECOVERY 105.5 101.3 72.67' 80.32 77.37 (X) 98 Table 6.5 - Catalyst Survey Results at 350°C SUBSTRATE SUPPORT NaOH Na3PO4 NaNO3 Na2HA504 ACRYLIC ACIo 0.93 12.3 13.98 22.69 21.06 (8.3) (32.9) (32.7) (41.8) (35.2) 2,3-PENTANEOIONE 0.64 9.05 7.76 12.6 14.28 (5.7) (24.2) (18.2) (23.21) (23.8) ACETALOEHYOE 8.96 7.39 8.51 9.2 11.3 (79.3) '(19.8) (19.9) (17) (18.9) PROPANOIC ACIO 0.76 3.49 5.72 1.8 2.04 (6.8) (9.3) (13.4) (3.3) (3.4) NYDROXYACETONE 0 4.63 5.89 7.08 9.41 (12.4) (13.8) (13) (15.7) OTHER 0 0.52 0.82 0.9 1.78 (1.4) (1.9) (1.7) (3) co \ 19.61 4.05 6.17 6.01 5.41 C02 2.8 20 28.52 31.89 33.71 CONVERSION (3) 38.95 65.8 90.63 91.94 ' 92.96 CARBON RECOVERY 81.82 80.94 64.15 73.05 . 78.23 a) CHAPTER 7 DISCUSSION AND CONCLUSIONS During lactic acid reaction studies, there were various experiments conducted in order to verify that the methods used for data analysis were correct and that the best possible results were obtained. 7.1 MASS BALANCE CONSIDERATIONS The concentration of feedstock lactic acid was a concern early in our studies. The assay from Purac for lactic acid concentration was 88 wt%. This concentrated solution was diluted with reverse osmosis (R0) water to 34 wt% lactic acid for each experimental run. As any error in lactic feed concentration would result in poor mass balances and incorrect product yields, two attempts were made to determine the actual lactic acid concentration. An attempt was made to determine the lactic acid concentration by means of pH analysis. The dissociation constant (Ka) of lactic at 25'C is approximately 1.37 x 104. Concentrated Purac and Aldrich lactic acid solutions were diluted.by factors of 10, 100 and 1000 to arrive at reasonable pH ranges. A Fisher Scientific Accumet 950 pH/ion meter was used to obtain data. Table 7.1 shows the results of the pH tests. It can be easily seen that these data are not very 99 100 reliable. The two lactic acid samples remained close in pH but they give results which are very different from the correct concentration, although the values at the loo-fold dilution are close. The reason for the scatter is unknown. The second method used to determine the lactic acid concentration was a carbon/hydrogen/nitrogen (CHN) test performed on a feed sample by the Michigan Biotechnology Institute. The sample was an 88 wt% lactic acid sample diluted to 34 wt%. The CHN results gave a carbon assay of 13.06 wt% carbon, which translates to a 32.7 wt% lactic acid solution. A 34 wt% lactic acid solution contains 13.60 wt% carbon. The error here is approximately 4%, which is too small to cause a large mass balance error. It was decided that the lactic acid feed concentration was close to 34 wt%. Table 7.1 - Lactic Acid pH Results DILUTION LACTIC ACID ‘ HTx pH CALCULATED LACTIC urx PURAC LACTIC ALDRICH LACTIC) PURAC LACTIC ALDRICH LACTIC 10 8.8 8.5 =:;I» '10.58 :9 14.99 100 0.88 0.85 0.74 0.83 1000 0.088 0.085 0.042 . ' 0.047 Gas Chromatograph response factors were calculated for all known reaction products using standards diluted to various 101 concentrations. These response factors are used to determine product concentrations based on the GC peak area for particular products. The old response factors were calculated in solutions which contained only one reaction product and the internal standard. This was not a correct representation of a product mixture, therefore, it was decided to combine various products to simulate product mixtures. It was necessary to recalculate the response factors for acrylic acid, 2,3-pentanedione, propanoic acid, hydroxyacetone, acetic Table 7.2 - Response Factors ! wasmce om news. m I Acetaldehyde 1.58 1.59 Acetic acid 2.08 1.95 Acetol 2.94 2.12 Acetone 1.07 0.98 “ Acrylic acid 1.34 1.22 Ethanol 1.37 1.10 Lactic acid 4.79 5.17 2,3-pantanediona 0.99 1.14 I Propanoic acid ' 1.21 1.11 acid, acetaldehyde, acetone, ethanol and lactic acid in a mixture. This check was performed in order to ensure that we VEI' Aga re: 91' be pr 08 fan The olc tog cor knc rat won the Pro was Prod Prod Was “Gut 102 were obtaining the best possible mass balances on the system. Again, 2-propanol was used as the internal standard. Table 7.2 shows the results of the response factor check. The response factors listed in the table are a ratio of the product GC area to the internal standard GC area. Most of the new response factors changed somewhere between 10 and 15%. To explain what this means in terms of product analysis, consider acrylic acid as an example. The new response factor is approximately 10% lower than the old. A concentration or yield calculated with the old response factor for acrylic acid would be 10% higher than with the new. The new response factors are probably more reliable than the old factors because solutions containing all reaction products together are similar to our reaction product mixtures. In order to determine if our analysis procedure was correct, we attempted to recreate a reaction product by adding known quantities of products to a lactic acid solution. Our rationale for doing this was to determine if the mass balance would be correct if a known product solution was run through the system. This test consisted of creating a reaction product solution, from standards, which simulated the product from one of our experimental runs. This liquid pseudo-product was run through the gas chromatograph and analyzed. Gas product concentrations were calculated based on the liquid product concentrations and a lactic acid feed concentration was calculated based on the total carbon content of the Pseudo-liquid and gas products. 103 Two previous runs were simulated; they were the 280°C and 320'C runs of NaZHAsO, supported on Spherosil XOC 005. Only the major reaction products were simulated (acetaldehyde, acrylic acid, 2,3-pentanedione, hydroxyacetone and lactic acid). Table 7.3 shows the results of our study. The run at 320‘C was performed twice due to the unacceptable carbon error found in the first run due to incorrect product concentration calculations. Hydroxyacetone was not included as a product for the second run. If our analysis procedure is exact, we would expect all GC calculated concentrations to be correct and there would be no carbon mass balance errors. One of the larger contributors to the carbon error is probably the lactic acid GC peak. Lactic acid is not very volatile and therefore, may be held up in our GC column. Since our conversion calculation is based on this peak, any errors would result in a carbon balance error. Carbon balance errors of 1-10% are very common and can be considered to be within experimental limits. Overall, this test went well and it suggests that our methods of data analysis are adequate for the scope of our studies. Mass balance closure has been a problem in the past and a great deal of time was spent minimizing this problem. Overall, mass balances improved very much over the course of the study. Recovery of 85 to 105% of the carbon introduced to the reactor has become the normal expectation of our system at reaction temperatures below 320'C. However, there are exceptions to this general rule. For instance, in many WT "' - . -. ' . Table 7.3 104 — Pseudo-Run Results RESULTS 280'C NaHAsO4 320‘C (1) NaHAsO4 320'C (2) NaHAsOlo I... ACRYLIC ACID YIELD 3.46 12.36 20.48 (X) 2,3°PENTANEDIONE 11.04 18.21 34.53 YIELD (X) ACETALDEHYDE YIELD 2.56 11.02 14.44 (X) ACETOL YIELD (X) 0.85 13.63 0.00 CONVERSION (x) 24.48 74.18 71.51 X CARBON ERROR -3.74 ~16.09 '7.83 105 experimental runs, a trend can be seen which implies that mass balances become worse as the reaction conversion increases and Table 7.4 shows this trend very well. The example used here is a NaNOS/silica catalyst run under short residence time Table 7.4 - Carbon Error Trends TEMPERATURE CONVERSION CARBON ERROR (x) 300 37.94 6.43 320 63.94 19.68 350 91.94 26.95 operating conditions (Table 1.3). High reaction temperatures usually exhibit - the greatest mass balance errors. The elevated mass balance errors are probably a result of a process or processes which more readily occur at higher reaction temperatures. 7.2 NECEANISTIC CONSIDERATIONS The microporosity of the supports used during our study seems to have been very important in determining product 106 selectivity and mass balance closure. Supports that possessed a more microporous structure seemed to form selectively more acetaldehyde and these supports also gave the poorest carbon recoveries. These are findings which seem to suggest that lactic acid cracking is taking place. For our studies, supports which do not exhibit extensive microporosity are recommended. Experimental runs produced carbon monoxide and carbon dioxide gas reaction products. As Figure 1.1 depicts, C02 is produced in the decarboxylation and condensation reactions of lactic acid while CO is produced in its decarbonylation. Production of CO, in our studies, is theoretically accompanied by acetaldehyde production. C02 can be accompanied by the production of acetaldehyde through decarboxylation or 2,3- pentanedione through condensation. In theory, the CO:C02 ratio shows the selectivity of the reaction towards the decarbonylation pathway versus the decarboxylation/ condensation pathways. Of these, only the condensation reaction mechanism is desired, therefore, CO:C02 ratios should be less than one for good results, although the decarboxylation pathway proves that a small ratio may not always produce desired results. 7 . 3 CONCLUSIONS Our studies produced a large quantity of data that contained very useful information. Although we have not yet 107 achieved a system'which could produce 2,3-pentanedione and/or acrylic acid. in. high enough. yields to 'warrant industry production, we have gone a long way in narrowing our search for a catalyst/support combination. Our study with the biomineral-derived calcium hydroxyapatite was first to show us the suppression of acetaldehyde due to a less microporous catalyst/support structure. The calcium hydroxyapatite runs with the material which had been calcined at higher temperatures showed this supression. This high calcination reduced the materials microporosity. We found also, however, that the production of the desired products was suppressed over the material calcined at the higher temperatures. Desired product yields over the calcium hydroxyapatite were not high enough to continue experimentation with them. The carbon supports, with the exception of the charred cherry pits, showed high product selectivity towards acetaldehyde. Suppression of the acetaldehyde yield occurred over'the charred cherry pits and also over Carbograph.2. Both of these materials have low surface areas and probably have little microporosity. The reaction product distribution of the charred cherry carbon was unlike the other carbon supports. .Acrylic acid, hydroxyacetone, and 2,3-pentanedione yields were very competitive with acetaldehyde and propanoic acid yields. The char has approximately 4% ash content, which Tnight have catalyzed the acrylic acid and/or 2,3-pentanedione formation. The silica supports showed the same trend in acetaldehyde 108 suppression. Those supports with the lower surface areas and suspected lower microporosity suppressed the production of acetaldehyde. The Spherosil XOC 005 gave the most promising results (Chapter 5) and was used for a catalyst screening. The best results were achieved by impregnating the XOC 005 silica with NazHAsO‘ (Chapter 6) but it was decided to discontinue use of this catalyst due to its extreme poisonous properties. The NaNOa/XOC 005 catalyst did a very good job suppressing acetaldehyde production and also showed good selectivity towards the desired products. It is recommended that a more in-depth study be done with this catalyst/support combination. This could consist of varying reaction parameters such as the loading, residence time, reactor pressure, etc. A more complete catalyst study would be necessary in order to determine how successful our experiments were. A look at more sodium compounds and possibly calcium compounds would definitely expand our knowledge of the chemistry and may improve our results. Improvements to the reactor system would also make experiments easier to conduct. On-line reaction product analysis could minimize the time between experiments and also would give insight on catalyst deactivation. An improved liquid feed mechanism and preheated zone would ensure lactic acid vaporization prior to catalyst contact which may have been a problem during our present studies. Overall, our study was successful and informative but there is a lot of work left to do in order to make our method 109 of lactic acid conversion to 2,3-pentanedione and/or acrylic .acid marketable. LIST OF REFERENCES 10. JLI 112 113 14 110 LIST OF REFERENCES Keeler, R., Research and Developement, 52 (February, 1991). Lipinsky, E.S., and R.G. Sinclair, Chem. Eng. Prog. 82(8), 25 (1986). Nakel, 6.11., and 8.14. Dirks, U.S. Patent #3,579,353 (1971). Maresca, L.M., U.S. Patent #4,611,033 (1986). Matsumoto, T., E. Yamada, O. Nakachi, and T. Komai, JP 61,243,807 (1986); (CA 106:138889k). Holmen, R.E., U.S. Patent #2,859,240 (1958). Paperizos, C., W. Shaw, 8. Dolhyl, (Standard Oil Co.), Catalytic Conversion of Lactic Acid and Ammonium Lactate to Acrylic Acid, EP 0 181 718 A2 (1986). Sawicki, R., (Texaco Inc.), Catalyst for Dehydration of Lactic Acid to Acrylic Acid, U.S. Patent #4,729,978 (1988). Odell, B., D. Earlam, Cole-Hamilton, Hydrothermal Reactions of Lactic Acid Catalysed by Group VIII Metal Complexes, J. Organometallic Chem. 290, 241-8 (1985). Velenyi, L.J. and S.R. Dolhyj, U.S. Patent #4,663,479 (1987). Sholin, A.F., V.V. Patrikeey, and A.A. Balandia, Dokl. Akad. Nauk. SSSR 173, 643 (1968). Fisher, C.H., and Filachione, E.M., Properties and Reactions of Lactic Acid, (1947). Mok, W.S.-Iu, M.J. Antal, Jr., and. M. Jones, Jr., Formation of Acrylic Acid from Lactic Acid in Supercritical Water, J. Org. Chem. 54, 4596 (1989). McCrackin, P.J., and C.T. Lira, Conversion.ofiLactic.Acid to Acrylic Acid in Supercritical Water, (1991). 15. 16. 17. 18. 111 Bett, J.A.S., L.G. Christner, and W. Keith Hall, Studies of the Hydrogen Held by Solids. XII. Hydroxyapatite Catalysts, J. Am. Chem. Soc. 89, 5535 (1957). Misono M., and W. Keith Hall, Oxidation-Reduction Properties of Copper- and Nickel-Substituted Hydroxyapatites, J. Phys. Chem. 77, 791 (1973). Boskey, A.L., and A.S. Posner, Formation of Hydroxyapatite at Low Supersaturation, J. Phys. Chem., 80, 40, (1976). Moffat, J.B., Phosphates as Catalysts, Catal. Rev.-Sci. Engr. 18(2), 199-258 (1978). APPENDIX 112 668 8.56586 260 . ..< 656.0 :5: «GEN—25n— mea SF 0.00 03 0:... 68.6 m _. . 6 O : 3:: .3: a , , H a M .2 W 23 ___M 0 , mom 1. E: _... 8 d E m E .. .. 8 m __ _. 8 m _ a 2. d _ 0 8 0 H 8 v W ./. m._._._.x0mn_>I . ZO_._.Dm_m._.m_n_ mN_m mea 113 008 06.56565 260 . «d 2.6.0 3.... 000.256 0000 8 30 0:... 68.6 m .o 0 I: .3: :._.::..:.: :: .. 3 .3 W _: _¢:_ 2: 0 cm I. : _: .7 w 8 d : _: _ .0 _ : .. .. 8 m _ 1 8 m _ a E d a 8 O .. w W ./. w.......x0m0>_.. . ZO_._.Dm_m._.m_n_ mN_m mmOn. 114 68.. 5.56.285 260 . a... 2.6.0 :5: mm...m.z<.o men. 8. 0.00 8.. 0:... 08... m .o O :::. ::EEEE: ::: .0 Wow W :_ E _: E: m z : .: :::. 0. won .I :: : - d 8 O _: _ 0 __ _ .. 0 oo 1. __ m _ E 3 8 M 8 cm 9 8.... W % m._._._.x0mn_>_.. . ZO.._.Dm_m._.m_n_ mum mmOn. 115 068 02.3.86 260 . ed 6590 .53 0005.56 0000 omp hmw mo; mp to wood M :::: E: :: .0 or W :_ _: : 0 : _ a w. on .I _ _ . e. o _ 0 om m on .I m on 3 8 M H. om 9 .d 2: V w ./. m._._._.x0mo>_._ - ZO_._.Dm_m_._.m.o mN.m mmOn. 116 062. 5.56520 260 - m.< 656.0 .50. 0005.50 0000 om.. 0......:_rF::._ 6;. m.....o oo_. % WVHO 33d BWR'IOA HHOd 'IVLNEWEHONI m.._._.x0mn_>_._ - ZO_._.Dm_m_._.m_n_ mN_m mmOn. 117 Oooo cozgzfio 9.00 . o.< 0.59“. .5... 0000.250 0000 wood o.. oN on oe om om on oo oo oo 0 % WVHO Had BWR'IOA 380d 'IVLNEIWEHONI m..._._.x0mo>I .. ZO_._.:m_m._.m_o NNE mmOn. 118 Table A.1 - Results for Calcium Hydroxyapatite calcined at 300°C _ A I C l 0 LE F 0 127 REPORT 128 Date 05/01/92 05/01/92 05/01/92 05/01/92 129 Update 06/02/93 06/02/93 06/02/93 06/02/93 130 Cat . Teeth Teeth Teeth Teeth 131 T(C) 280.000 300.000 350.000 280.000 132 mm 7.320 7.378 7.374 7.709 133 Err(XC) -19.196 -1.312 -30.248 -25.497 134 Conv(80F) 31.285 35.809 77.602 72.126 135 Yld 805(2) 136 Acryl 1.522 8.469 14.795 2.068 137 Prop 1.000 1.939 9.013 4.406 138' 239 1.403 2.381 .468 3.998 139 Acetal 2.341 7.027 13.875 26.143 140 0th 1.943 8.129 8.762 3.827 141 Unknom 4.763 9.670 4.181 14.351 142 Unacct 18.314 -1.806 26.507 17.334 143 00' .390 .870 4.308 4.536 144 002* 1.951 2.805 5.946 4.012 145 Yld 80C“) 146 Acryl 4.863 23.650 19.066 2.867 147 Prop 3.195 5.414 11.614 6.109 148 231’ 4.485 6.650 .603 5.542 149 Acetal 7.484 19.625 17.880 36.246 150 0th 6.211 22.701 11.291 5.305 151 Unknown 15.223 27.003 5.388 19.897 152 Unacct 58.538 -5.042 34.158 24.033 153 00" 1.247 2.429 5.552 6.289 154 002* 6.237 7.833 7.662 5.563 155 Achth 8.058 29.064 30.680 8.976 156 Aer/Pth 60.352 81.374 62.144 31.942 119 Table A.2 - Results for Calcium Hydroxyapatite calcined at 400°C A l 8 1 c I D I E I F I G 127 REPORT 128 Date 05/14/92 05/14/92 05/14/92 05/14/92 129 Update 06/02/93 06/02/93 06/02/93 06/02/93 130 Cat. Teeth Teeth Teeth Teeth 131 T(C) 280.000 300.000 320.000 280.000 132 RT“) 4.416 4.385 4.261 4.501 133 Err(XC) -13.393 -5.148 -8.583 -13.295 134 Conv(80F) 20.493 19.319 43.073 19.706 135 Yld BOP“) 136 Acryl 2.325 5.909 17.152 2.801 137 Prop .394 .762 1.880 .447 138 23P 1.181 1.550 1.729 .637 139 Acetal 2.161 4.483 9.627 1.155 140 0th 1.237 1.894 3.970 1.196 141 Unknown .000 .000 1.063 .000 142 Unecct 13.196 4.721 7.651 13.470 143 00" .621 2.196 4.690 .552 144 002' 2.054 2.180 4.152 1.825 145 Yld 8°C“) 146 Acryl 11.346 30.587 39.822 14.215 147 Prop 1.921 3.944 4.364 2.267 148 23P 5.763 8.023 4.015 3.233 149 Acetel 10.543 23.203 22.350 5.862 150 0th 6.036 9.804 9.218 6.068 151 Unknom .000 .000 2.468 .000 152 Unacct 64.390 24.440 17.764 68.355 153 00* 3.030 11.367 10.889 2.801 154 002* 10.021 11.282 9.640 9.263 155 Achth 13.267 34.531 44.186 16.482 156 Acr/Pth 85.520 88.578 90.123 86.244 120 Table A.3 - Results for Calcium Hydroxyapatite calcined at 500°C _; A 8 1 c 1 0 e F r 0 127 REPORT 128 Date 05/18/92 05/18/92 05/18/92 05/18/92 129 Update 06/02/93 06/02/93 06/02/93 06/02/93 130 Cat . Teeth Teeth Teeth Teeth 131 1(0) 280.000 300.000 320.000 280.000 132 RT(s) 5.544 5.304 5.069 5.450 133 arrow) -.658 43.073 -29.191 -6.437 134 Conv(80F) 3.645 19.820 43.516 10.459 135 Yld sown 136 Acryl 1.389 3.701 8.621 2.074 137 Prop .000 .191 .300 .000 138 23P .529 .562 .656 .327 139 Acetal 1.106 1.261 2.599 .575 140 0th .000 1 .071 1 .434 .000 141 Unknown .000 .000 .000 .000 142 Unacct .621 13.035 29.906 7.483 143 00" .583 1.022 1.885 .591 144 002* .675 .705 3.461 3.282 145 Yld 800m 146 Acryl 38.110 18.675 19.811 19.834 147 Prop .000 .962 .690 .000 148 23P 14.515 2.835 1.508 3.126 149 Acetal 30.346 6.361 5.972 5.498 150 0th .000 5.402 3.295 .000 151 Unknown .000 .000 .000 .000 152 Unacct 17.029 65 .765 68.723 71.542 153 00* 15.993 5.157 4.333 5.653 154 002* 18.514 3.557 7.953 31.384 155 Achth 38.110 19.637 20.501 19.834 156 Aer/Pth 100.000 95.100 96.634 100.000 121 Table A.4 - Results for Calcium Hydroxyapatite calcined at 600°C __ A 1 0 1 0 1 s 1 r 1 0 127 REPORT 128 Date 05/28/92 05/28/92 05/28/92 05/28/92 129 Update 06/02/93 06/02/93 06/02/93 06/02/93 130 Cat. Teeth Teeth Teeth Teeth 131 1(0) 280.000 300.000 320.000 280.000 132 111(3) 5.476 5.447 5.237 5.500 133 Errata) 3.245 . -2.790 -20.961 -3.398 134 COM/(BOP) 1.046 11.327 37.950 7.870 135 Yld 80H!) 136 Acryl 1.154 3.142 7.130 2.017 137 Prop .000 .182 .396 .000 138 23P .487 1.103 1.478 .546 139 Acetal .710 1.702 4.335 .638 140 0th 2.386 2.133 3.027 1.219 141 Unknom .000 .000 .000 .000 142 Unecct -3.691 3.066 21.584 3.450 143 00* .936 1.841 4.454 .798 144 002* 1.064 2.379 3.865 .908 145 Yld 800(1) 146 Acryl 110.309 27.737 18.788 25.625 147 Prop .000 1.603 1.043 .000 148 23P 46.541 9.736 3.894 6.942 149 Acetal 67.874 15.030 11.424 8.113 150 0th 228.077 18.827 7.977 15.484 151 Unknown .000 .000 .000 .000 152 Unocct -352.801 27.067 56.874 43.836 153 00* 89.479 16.252 11.738 10.144 154 002* 101.719 21.001 10.185 11.531 155 Achth 110.309 29.341 19.831 25.625 156 Acr/Pth 100.000 94.535 94.742 100.000 122 Table A.5 - Results for Calcium Hydroxyapatite calcined at 700°C __ A a 1 c 1 0 e r j 0 127 REPORT 128 Date 05/19/92 05/19/92 05/19/92 05/19/92 129 Update 06/02/93 06/02/93 06/02/93 06/02/93 130 Cat . Teeth Teeth Teeth Teeth 131 1(0) 280.000 300.000 320.000 280.000 132 111(3) 5.199 5.255 5.255 5.533 133 arrow) 2.705 -3.303 ~19.216 -6.457 134 Com/(80F) .355 10.928 35.177 10.076 135 Yld 80F(x) 136 Acryl ' .929 2.361 6.006 1.275 137 Prop .000 .249 .569 .000 138 23? 1.132 1.756 2.726 .911 139 Acetal .729 1.280 3.513 .406 140 0th .000 1.221 2.716 .672 141 Unknown .000 .000 .000 .000 142 Unacct -2.435 4.062 19.648 6.810 143 00* .779 1.163 2.098 .712 144 002* 1.326 3.271 4.407 1.210 145 11:! 800(2) 146 Acryl 261.600 21.605 17.073 12.657 147 Prop .000 2.279 1.616 .000 148 23P 318.469 16.070 7.751 9.043 149 Acetel 205.194 11.710 9.985 4.034 150 0th .000 11.169 7.722 6.673 151 Unknown .000 .000 .000 .000 152 Unecct -685.263 37.167 55.853 67.593 153 00* 219.336 10.642 5.963 7.062 154 002* 373.062 29.935 12.527 12.011 155 Achth 261.600 23.884 18.690 12.657 156 Acr/Pth 100.000 90.457 91 .353 100.000 123 Table A.6 - Results for Calcium Hydroxyapatite calcined at 800°C A 8 1 0 I 0 [ E 1 F 1 G 127 REPORT 128 Date 05/08/92 05/08/92 05/08/92 05/08/92 129 Update 10/25/92 10/25/92 10/25/92 10/25/92 130 Cat. Teeth Teeth Teeth Teeth 131 1(0) 280.000 300.000 320.000 280.000 132 RT(s) 5.042 4.941 4.731 4.944 133 Err(%C) -1.727 -3.476 -1s.560 -7.369 134 Conv(80F) 4.447 9.678 31.976 11.185 135 1116 80m) 136 Acryl .557 1.378 3.714 .725 137 Prop .252 .742 2.511 .605 138 23P .706 1.643 2.855 .757 139 Acetal .718 1.443 4.159 1.146 140 0th .446 1.351 3.059 .634 141 Unknown .000 .000 .000 .000 142 Unecct 1.769 3.121 15.678 7.319 143 00* .762 .727 2.139 .636 144 002* .882 .811 4.308 .737 145 Yld 800(8) 146 Acryl 12.519 14.243 11.615 6.478 147 Prop 5.673 7.667 7.854 5.412 148 23P 15.872 16.978 8.928 6.765 149 Acetel 16.137 14.908 13.007 10.244 150 0th 10.020 13.959 9.567 5.668 151 Unknown .000 .000 .000 .000 152 Unecct 39.779 32.246 49.030 65.434 153 00* 17.125 7.514 6.689 5.689 154 002* 19.834 8.377 13.474 6.589 155 Achth 18.192 21.910 19.469 11.890 156 Acr/Pth 68.817 65.007 59.660 54.481 - Results for Calcium Hydroxyapatite 124 Table A.7 10 x 16 mesh particle size A B 1 0 I 0 a F 127 REPORT 128 Date 09/16/92 09/16/92 09/16/92 129 Update 06/02/93 06/02/93 06/02/93 130 Cat. Teeth Teeth Teeth 131 1(0) 280.000 300.000 320.000 132 RT(s) 6.679 6.406 6.232 133 £rr(20) .278 5.556 -13.657 134 ConV(BOF) 24.517 34.829 74.316 135 Yld 80P(2) 136 Acryl 2.960 8.865 23.140 137 Prop 2.211 2.589 4.106 138 23P 1.847 2.903 2.050 139 Acetal 4.959 9.883 17.222 140 0th 1.245 2.487 3.519 141 Unknown 12.913 15.698 12.166 142 Unacct -1.619 -7.596 12.112 143 00* 1.106 2.720 8.729 144 002* 2.023 4.402 8.422 145 Yld 800(2) 146 Acryl 12.074 25.454 31.138 147 Prop 9.020 7.434 5.525 148 23P 7.534 8.335 2.758 149 Aoetal 20.228 28.377 23.174 150 0th 5.079 7.140 4.735 151 Unknown 52.670 45.070 16.371 152 Unacct -6.605 -21.810 16.299 153 00* 4.510 7.810 11.746 154 002* 8.253 12.637 11.332 155 Achth 21.094 32.888 36.663 156 Acr/Pth 57.238 77.395 84.930 Rte. 125 Table A.8 - Results for Calcium Hydroxyapatite 16 x 30 mesh particle size A I 8 F c | 0 l E 1 r 127 REPORT 128 Date 9/22/92 9/22/92 9/22/92 129 Update 06/02/93 06/02/93 06/02/93 130 Cat. Teeth Teeth Teeth 131 1(0) 280.000 300.000 320.000 132 mm 5.629 5.781 5.500 133 Err(XC) -9.447 6.864 3.397 134 Com/(80F) 28.935 23.591 51.219 135 no 80r(2) 136 Acryl 2.627 7.164 22.146 137 Prop 1.016 1.251 2.597 138 23P 2.800 3.197 3.230 139 Acetal 4.180 6.917 12.443 140 0th .860 2.496 4.725 141 Unknown 8.613 6.243 9.840 142 Unecct 8.840 -3.678 -3.762 143 00* 1.415 10.112 7.745 144 002* 3.616 9.455 8.330 145 Yld 800(2) 146 Acryl 9.078 30.368 43.237 147 Prop 3.512 5.305 5.070 148 23P 9.677 13.553 6.307 149 Acetel 14.445 29.319 24.294 150 0th 2.972 10.582 9.224 151 Unknown 29.766 26.464 19.212 152 Unacct 30.550 -15.591 -7.344 153 00* 4.890 42.865 15.121 154 002* 12.496 40.080 16.263 155 Achth 12.590 35.673 48.307 156 Aer/Pth 72.106 85.130 89.505 126 Table A.9 - Results for Calcium Hydroxyapatite 30 x 60 mesh particle size A 8 I c I 0 e F 127 REPORT 128 note 9/29/92 9/29/92 9/29/92 129 Update 10/20/92 10/20/92 10/20/92 130 Cat. Teeth Teeth Teeth 131 1(0) 280.000 300.000 320.000 132 ms) 5.150 5.486 5.378 133 Err(20) -1.525 -.376 -2.324 134 Conv(80F) 17.653 29.767 48.946 135 no mm 136 Acryl 1.998 6.062 17.900 137 Prop .887 1.215 2.099 138 23P 2.117 3.147 3.234 139 Acetal 2.654 4.242 9.348 140 0th .841 2.761 5.638 141 Unknown 8.023 12.027 10.262 142 Unacct 1.134 .312 .466 143 00* 1.063 2.671 3.386 144 002* 2.335 4.809 4.673 145 Yld 800(2) 146 Acryl 11.317 20.366 36.570 147 Prop 5.023 4.082 4.288 148 23P 11.991 10.573 6.608 149 Acetel 15.031 14.251 19.098 150 0th 4.762 9.276 11.519 151 Unknown 45.451 40.405 20.965 152 Unacct 6.425 1.047 .952 153 00* 6.024 8.972 6.917 154 002* 13.229 16.155 9.547 155 Achth 16.340 24.448 40.858 156 Aer/Pth 69.259 83.303 89.506 127 Table A.1O - Results for Strem Activated Carbon A I 8 I 0 I D I E I F I G 127 REPORT 128 Date 11/17/92 11/17/92 11/17/92 11/17/92 129 Update 02/17/93 02/17/93 02/17/93 02/17/93 130 Cat. Carbon Carbon Carbon Carbon 131 T(C) 280.000 300.000 320.000 350.000 132 RT(8) 6.202 5.980 5.829 5.500 133 ErraC) -2.249 -36.755 -30.120 -32.155 134 Conv(BOF) 82.437 85.861 94.672 94.571 135 Yld BOP“) 136 Acryl .279 .840 .399 .397 137 Prop 20.593 10.599 14.186 15.383 138 23P .000 .606 .274 .251 139 Acetal 41.588 17.366 30.925 22.427 140 0th 7.940 6.199 8.341 9.210 141 Unknown 8.239 5.686 6.373 6.962 142 Unacct 3.799 44.566 34.174 39.942 143 00' 33.805 27.427 29.325 30.844 144 002' 21.364 20.649 24.370 28.167 145 Yld 80C“) 146 Acryl .338 .978 .421 .420 147 Prop 24.980 12.344 14.985 16.266 148 23P .000 .706 .289 .266 149 Acetal 50.448 20.226 32.666 23.714 150 0th 9.631 7.220 8.810 9.738 151 Unknom 9.994 6.623 6.732 7.361 152 Unacct 4.608 51.904 36.097 42.234 153 00* 41.007 31.943 30.975 32.615 154 002* 25.916 24.049 25.742 29.784 155 Achth 25.318 13.322 15.406 16.686 156 Aer/Pth 1.337 7.340 2.734 2.517 Table A.11 128 Results for Na3P04 on Strem Carbon _ A 0 0 e I r I 0 127 REPORT 128 Date 11/24/92 11/24/92 11/24/92 11/24/92 129 Update 12/02/92 12/02/92 12/02/92 12/02/92 130 Cat. 11de Na3PO4 N83P04 wa3Po4 131 1(0) 280.000 300.000 320.000 350.000 132 mm 5.837 5.578 5.774 5.484 133 Err(20) -1.769 -13.749 -21.358 -26.961 134 Conv(80F) 52.812 77.881 87.422 96.306 135 Yld 80r(2) 136 Acryt .872 1.386 1.363 .244 137 Prop 16.486 22.132 27.027 23.510 138 23P .114 .142 .315 .290 139 Acetel 14.159 13.234 12.459 20.253 140 0th 5.382 7.063 7.496 7.635 141 Unknown 8.825 8.854 7.957 6.626 142 Unacct 6.973 25.071 30.806 37.749 143 00* 12.439 20.144 15.727 23.221 144 002* 21.619 33.306 33.400 40.154 145 no 800(2) 146 Acryl 1.651 1.779 1.559 .253 147 Prop 31.217 28.417 30.915 24.412 148 23P .216 .183 .361 .301 149 Acetal 26.811 16.992 14.252 21.030 150 0th 10.191 9.068 8.574 7.928 151 Unknown 16.710 11.369 9.102 6.880 152 Unecct 13.204 32.191 35.238 39.197 153 CO' 23.554 25.865 17.989 24.111 154 002* 40.937 42.765 38.205 41.694 155 Achth 32.868 30.196 32.474 24.665 156 AcrlPth 5.023 5 .891 4.799 1.026 Results for the Activated Cherry Carbon 129 Table A.12 - A 8 I c I D j E I F 127 REPORT 128 Date 1/14/93 1/14/93 1/14/93 129 Update 02/17/93 02/17/93 02/17/93 130 Cat. cherry cherry cherry 131 NC) 280.000 300.000 320.000 132 RT(8) 6.033 5.864 5.539 133 Err(%C) -17.324 -31.981 -30.454 134 Conv(80F) 83.370 86.262 83.999 135 Yld 80F“) 136 Acryl .437 .635 .826 137 Prop 7.253 6.199 8.622 138 23P .781 .541 .554 139 Acetal 34.219 25.145 23.494 140 0th 3.320 3.694 5.321 141 Unknown 8.233 7.136 8.893 142 Unacct 29.127 42.913 36.289 143 00* 52.287 45 .859 27.656 144 002‘ 22.097 16.971 19.708 145 Yld 800(2) 146 Acryl .524 .737 .984 147 Prop 8.699 7.186 10.264 148 23P .936 .627 .660 149 Acetal 41.045 29.150 27.969 150 0th 3.983 4.282 6.335 151 Unknown 9.875 8.272 10.587 152 Unacct 34.938 49.747 43.201 153 00" 62.717 53.163 32.924 154 002' 26.504 19.674 23.463 155 Achth 9.223 7.922 11.248 156 Acr/Pth 5.681 9.297 8.747 Table A.13 Results for the Charred Cherry Pits 130 A I C I D E F G 127 REPORT 128 Date 01/26/93 01/26/93 01/26/93 01/26/93 129 Update 02/17/93 02/17/93 02/17/93 02/17/93 130 Cat . Carbon Carbon Carbon Carbon 131 T(C) 280.000 300.000 320.000 350.000 132 RT(8) 5.610 5.499 5.432 5.152 133 Err(%C) -33.255 -4.911 -22.859 -28.797 134 Conv(BOF) 58.199 38.509 75.455 92.511 135 Yld 80“!) 136 Acryl .995 3.099 6.615 3.976 137 Prop 3.156 4.638 9.303 14.365 138 23P 1.868 7.987 7.763 2.851 139 Acetal 3.310 4.191 5.016 9.401 140 0th 2.227 3.725 6.325 6.954 141 Unknown 8.274 6.374 8.866 14.893 142 Unacct 38.368 8.494 31.567 40.071 143 00* 5.353 1.011 4.037 8.124 144 002‘ 16.458 19.541 32.749 41.387 145 Yld 800(2) 146 Acryl 1.710 8.048 8.766 4.298 147 Prop 5.423 12.045 12.329 15.528 148 23P 3.210 20.741 10.288 3.081 149 Acetal 5.688 10.883 6.648 10.162 150 0th 3.827 9.674 8.382 7.517 151 Unknown 14.216 16.552 11.750 16.099 152 Unacct 65.925 22.057 41.836 43.315 153 00* 9.199 2.626 5.350 8.782 154 1232' 28.278 50.745 43.402 44.737 155 Achth 7.134 20.093 21.095 19.826 156 Aer/Pth 23.976 40.055 41.556 21.679 "e‘LJl'.-_ 3w 131 Table A.14 - Results for Na3PO4 on the Cherry Char __ A I 8 I c I D I E I F I G 127 REPORT 128 Date 02/04/93 02/04/93 02/04/93 02/04/93 129 Update 02/05/93 02/05/93 02/05/93 02/05/93 130 Cat . Na3PO4 Na3P04 Na3P04 Na3P04 131 T(C) 280.000 300.000 320.000 350.000 132 RT(8) 8.212 8.030 7.881 7.666 133 Err(%C) -19.095 -14.590 -16.433 -25.271 134 Com/(80F) 44.344 63.099 80.475 92.298 135 Yld 80F“) 136 Acryl 2.382 6.856 12.542 9.768 137 Prop 1.991 2.715 5.750 10.958 138 23P 1.688 7.041 8.847 3.661 139 Acetal 1.689 4.351 4.741 7.380 140 0th 1.461 4.577 8.212 6.574 141 Unknown 13.818 16.273 8.809 11.018 142 Unacct 21.315 21.286 31.573 42.938 143 00" .836 2.787 7.780 9.740 144 002* 8.814 26.195 47.833 54.896 145 Yld 80C“) 146 Acryl 5.371 10.866 15.585 10.583 147 Prop 4.491 4.302 7.146 11.873 148 23P 3.806 11.158 10.994 3.966 149 Acetal 3.808 6.895 5.891 7.996 150 0th 3.296 7.254 10.204 7.123 151 Unknown 31.161 25.790 10.947 11.938 152 Una00t 48.067 33.734 39.233 46.521 153 00' 1.886 4.417 9.667 10.553 154 002* 19.876 41.514 59.438 59.477 155 Achth 9.862 15.168 22.731 22.456 156 Acr/Pth 54.464 71.636 68.564 47.128 132 Table A.15 - Results for Carbograph 1 __ A I 8 I 0 I 0 I E I F I 0 127 REPORT 128 Date 02/22193 02/22/93 02/22/93 02/22/93 129 Update 02/26/93 02/26/93 02/26/93 02/26/93 130 Cat. carbo 1 carbo 1 carbo 1 carbo 1 131 T(C) 280.000 300.000 320.000 350.000 132 RT(8) 7.329 7.135 6.967 6.789 133 Err(%C) -.961 2.440 -12.784 -29.800 134 Conv(80F) 13.296 22.118 48.196 75.012 135 Yld 80F“) 136 Acryl .247 .324 .706 .848 137 Prop 1.152 2.085 4.319 7.511 138 23P .000 .112 .157 .392 139 Acetal 3.373 5.938 11.993 17.400 140 0th .297 .459 .252 1 .399 141 Unknown 2.538 9.712 12.341 5.684 142 Unacct 5.689 3.488 18.428 41.779 143 00" 16.113 17.676 14.051 18.966 144 002' 1.742 6.560 15.206 36.095 145 Yld 80C“) 146 Acryl 1.856 1.466 1.465 1.131 147 Prop 8.662 9.428 8.961 10.013 148 23P .000 .505 .326 .523 149 Acetal 25.368 26.849 24.883 23.196 150 0th 2.233 2.073 .523 1.865 151 Unknown 19.092 43.910 25.606 7.577 152 Unacct 42.788 15.770 38.236 55.696 153 00‘ 121.188 79.916 29.153 25.284 154 002* 13.101 29.660 31.551 48.118 155 Achth 10.518 10.894 10.426 11.144 156 A0r/Pth 17.647 13.454 14.051 10.146 133 Table A.16 - Results for Carbograph 2 A I B I C I D I E I F I 0 Date 03/03/93 03/03/93 03/03/93 03/03/93 Update Cat. carbo 2 T(C) 280.000 RTts) 6.170 Err(XC) 5.516 Conv(80F) 3.528 Yld 80F(X) Acryl .540 Prop .723 23P .045 Acetal 2.109 0th .498 Unknown 4.057 Unacct -4.445 00* 2.993 002* 2.848 Yld 800(1) Acryl 15.307 Prop 20.504 23P 1.272 Acetal 59.777 0th 14.122 Unknown 115.003 Unacct -125.985 C0* 84.845 002* 80.734 A0rPth 35.811 Aer/Pth 42.745 carbo 2 300.000 5.926 -13.649 23.726 .961 1.396 .072 2.840 .360 3.273 14.825 3.717 3.047 4.049 5.883 .304 11.972 1.516 13.795 62.482 15.667 12.843 9.932 40.765 carbo 2 320.000 5.802 *13.205 40.988 .492 3.101 .167 5.594 2.113 13.283 16.239 5.957 9.627 1.199 7.566 .406 13.648 5.155 32.407 39.619 14.533 23.488 8.765 13.682 03/10/93 03/10/93 03/10/93 03/10/93 carbo 2 350.000 5.604 -7.728 60.507 .832 10.218 .644 16.470 7.213 11.311 13.819 10.195 27.739 1.376 16.887 1.064 27.219 11.921 18.694 22.839 16.850 45.844 18.262 7.533 134 Table A.1? - Results for the 1 mm diameter glass beads A I 8 I C I D I E I F 127 REPORT 128 Date 10/08/92 10/08/92 10/08/92 129 Update 10/21/92 10/21/92 10/21/92 130 Cat. Glass Glass Glass 131 T(C) 280.000 300.000 320.000 132 RT(8) 5.523 5.469 5.405 133 Err(%C) 1.242 -1.922 4.512 134 Conv(BOF) 5.094 10.054 11.048 135 Yld 80F(X) 136 Acryl .227 .753 2.316 137 Prop .582 .850 1.518 138 23P .314 .853 2.255 139 Acetal .380 1.009 2.287 140 0th .000 .000 1.446 141 Unknown 4.633 4.446 5.607 142 Unacct -1.042 2.143 -4.380 143 CO‘ .252 .440 .868 144 C02‘ .886 1.658 2.942 145 Yld 800(1) 146 . Aoryl 4.447 7.492 20.959 147 Prop 11.426 8.457 13.735 148 23P 6.160 8.483 20.407 149 Acetal 7.466 10.034 20.703 150 0th .000 .000 13.090 151 Unknown 90.954 44.223 50.753 152 Unacct -20.454 21.311 -39.648 153 C0* 4.953 4.380 7.861 154 C02* 17.400 16.489 26.631 155 A0rPth 15.874 15.949 34.695 156 A0r/Pth 28.017 46.973 60.411 135 Table A.18 - Results for the Silica Gel A I 8 I 0 I D I E I F 7 6 REPORT Date 12/12/92 12/12/92 12/12/92 12/12/92 Update 02/17/93 02/17/93 02/17/93 02/17/93 Cat. Silica Silica Silica Silica T( C) 280.000 300.000 320.000 350.000 RT(s) 5.892 5.757 5.690 5.418 Err(XC) -22.378 -17.386 -33.331 -31.731 Conv(80F) 41.559 40.296 64.767 87.179 Yld 80F“) Acryl .340 .673 1.617 3.879 Prop .894 .787 1.278 4.162 23P .210 .362 .713 1.699 Acetal 11.736 17.808 26.247 46.516 0th .645 .234 .995 3.027 Unknown 4.217 3.258 2.481 2.994 Unacct 23.517 17.175 31.436 24.901 00* 14.237 16.578 19.941 25.231 002* 1.667 1.011 - 2.277 5.101 Yld 80C“) Acryl .819 1.670 2.497 4.450 Prop 2.150 1.953 1.974 4.775 23P .505 .898 1.101 1.949 Acetal 28. 238 44 .193 40. 525 53 .357 0th 1 .553 .580 1.537 3.472 Unknown 10.148 8.085 3.831 3.435 Unacct 56.587 42.621 48.537 28.563 00* 34.256 41.140 30.788 28.941 002* 4.012 2.509 3.516 5.851 A0rPth 2.969 3.622 4.470 9.224 AcrlPth 27.580 46.092 55.847 48.238 136 Table A.19 - Results for the Calcined Silica Gel A 8 I 0 I 0 e I r I 0 127 REPORT 128 Date 01/28/93 01/28/93 01/28/93 01/28/93 129 Update 02/17/93 02/17/93 02/17/93 02/17/93 130 Cat. silica silica silica silica 131 1(0) 280.000 300.000 320.000 350.000 132 RT“) 5.746 5.624 5.541 5.273 133 Err(20) -25.381 -19.787 .987 -28.712 134 Conv(80F) 47.617 52.721 54.246 83.241 135 Yld 80P(2) 136 Acryl .329 .751 1.931 2.924 137 Prop .544 1.345 2.808 8.388 138 23P .423 .290 1.092 1.072 139 Acetal 17.901 25.234 37.964 22.634 140 0th .428 .000 2.115 5.385 141 Unknown 2.793 3.962 4.868 6.281 142 Unacct 25.200 21.139 3.468 36.556 143 00* 15.010 25.116 45.133 32.500 144 002* 2.985 4.316 8.169 17.726 145 Yld 800(2) 146 Acryl .692 1.425 3.559 3.512 147 Prop 1.143 2.551 5.176 10.076 148 23P .887 .550 2.014 1.288 149 Acetal 37.593 47.862 69.985 27.191 150 0th .898 .000 3.899 6.469 151 Unknown 5.866 7.516 8.975 7.545 152 Unacct 52.922 40.095 6.393 43.917 153 00* 31.523 47.639 83.200 39.043 154 002* 6.269 8.187 15.059 21.295 155 A0rPth 1.834 3.976 8.735 13.589 156 Acr/Pth 37.718 35.846 40.744 25.848 137 Table A.20 - Results for the XOA 400 Silica A I I 0 I D I E I F I G 127 REPORT 128 Date 03/06/93 03/06/93 03/06/93 03/06/93 129 Update 03/10/93 03/10/93 03/10/93 03/10/93 130 Cat. x0A 400 11011 400 x0A 400 XOA 400 131 1(0) 280.000 300.000 320.000 350.000 132 RT(8) 8.386 7.522 7.350 7.031 133 Err(20) 20.285 -8.311 -28.139 -33.151 134 Com/(80F) 65.408 88.231 96.080 95.866 135 no 80F(2) 136 Acryl .155 .329 .803 .996 137 Prop .549 1.034 2.744 7.121 138 23P .183 .259 .305 .212 139 Acetal 67.334 61.121 54.504 34.407 140 0th 1.809 2.422 2.824 4.426 141 Unknown 6.569 8.647 3.848 6.965 142 Unacct -11.191 14.418 31.051 41.738 143 00* 92.547 74.570 51.886 34.151 144 002* 3.252 7.081 14.128 29.996 145 Yld 800(2) 146 Acryl .237 .373 .836 1.039 147 Prop .839 1.172 2.856 7.428 148 23P .280 .294 .317 .221 149 Acetal 102.945 69.274 56.728 35.891 150 0th 2.766 2.745 2.940 4.617 151 Unknown 10.044 9.800 4.005 7.265 152 Unacct ~17.109 16.342 32.318 43.538 153 00* 141.491 84.516 54.004 35.624 154 002* 4.971 8.025 14.705 31.290 155 A0rPth 1.076 1.545 3.693 8.468 156 Acr/Pth 22.007 24.133 22.646 12.275 138 Table A.21 - Results for the XOB 030 Silica __ A 1 0 I 0 I e l r 1 0 127 REPORT 128 Date 03/09/93 03/09/93 03/09/93 03/09/93 129 Update 03/10/93 03/10/93 03/10/93 03/10/93 130 cat. me 030 x08 030 me 030 208 030 131 1(0) 280.000 300.000 320.000 350.000 132 RT(s) 6.823 6.683 6.314 6.227 133 £rr(20) 2.455 -11.571 -26.696 -23.880 134 Conv(80F) 13.715 37.613 63.496 88.779 135 Yld mm 136 Acryl .207 1.036 2.730 4.985 137 Prop .974 1.706 4.247 11.041 138 23P .335 .841 1.932 3.294 139 Acetal 8.462 13.356 22.950 36.013 140 0th .334 .308 .678 1.877 141 Unknom 3.693 7.163 4.339 6.694 142 Unacct -.290 13.203 26.621 24.874 143 00* 13.233 15.740 18.762 26.489 144 002* 2.226 3.240 5.831 16.424 145 Yld 800(2) 146 Acryl 1.507 2.755 4.299 5.615 147 Prop 7.103 4.536 6.688 12.437 148 23P 2.443 2.236 3.043 3.710 149 Acetal 61.704 35 .508 36.144 40.565 150 0th 2.436 .818 1.068 2.114 151 Unknown 26.924 19.045 6.833 7.541 152 Unacct -2.117 35.102 41.925 28.018 153 00* 96.488 41.847 29.548 29.838 154 002* 16.229 8.615 9.184 18.500 155 A0rPth 8.610 7.291 10.987 18.052 156 Acr/Pth 17.506 37.790 39.127 31.105 139 Table A.22 - Results for the XOC 005 Silica A I I 0 I D E I F G 127 REPORT 128 Date 03/12/93 03/12/93 03/12/93 03/12/93 129 Update 03/12/93 03/12/93 03/12/93 03/12/93 130 Cat. 1100 005 x00 005 200 005 200 005 131 1(0) 280.000 300.000 320.000 350.000 132 81(8) 6.585 6.268 6.072 5.917 133 Err(20) 8.261 -5.251 -32.060 -46.973 134 Conv(80F) 4.686 18.911 52.456 86.818 135 Yld 808(2) 136 Acryl .252 .267 .794 1.682 137 Prop .559 .453 1 .767 5 .782 138 23P .099 .219 .683 1.341 139 Acetal 4.666 4.564 10.326 13.650 140 0th .517 .000 .649 ‘ 1.654 141 Unknown 3.069 8.252 5.986 7.323 142 Unacct -4.476 5.156 32.251 55.387 143 00* 9.081 3.455 7.939 18.262 144 002* 7.507 .934 3.952 23.246 145 Yld 800(2) 146 Acryl 5.379 1.412 1.513 1.937 147 Prop 11.925 2.396 3.369 6.660 148 23P 2.103 1.158 1.303 1.545 149 Acetal 99.586 24.136 19.685 15.722 150 0th 11.028 .000 1.236 1.905 151 Unknown 65.502 43.637 11.412 8.435 152 Unacct -95.523 27.262 61.483 63.796 153 00* 193.794 18.267 15.135 21.034 154 002* 160.206 4.937 7.533 26.776 155 A0rPth 17.304 3.808 4.881 8.597 156 Aer/Pth 31.085 37.086 30.990 22.531 A A! 140 Table A.23 - Results for the XOC 005 Silica (short residence time) A I 0 I 0 I E I F I 8 127 REPORT 128 Date 04/06/93 04/06/93 04/06/93 04/06/93 129 Update 04l07/93 04/07/93 04/07/93 04l07/93 130 Cat. 200 005 200 005 200 005 200 005 131 T(C) 280 300 320 350 132 RT(8) 1.991 1.933 1.905 1.816 133 Err(XC) -14.793 2.680 5.500 -18.181 134 Conv(80F) 18.838 4.056 5.150 38.954 135 Yld 80F(2 136 Acryl .224 .210 .288 .934 137 Prop .377 .381 .336 .763 138 23P .033 .138 .197 .644 139 Acetal .588 .956 2.964 8.962 140 0th .436 .391 .000 .000 141 Unknown 2.407 4.479 5.877 5.097 142 Unacct 14.772 -2.501 -4.510 22.555 143 1:0" .521 1.280 4.721 19.608 144 002' .458 .675 1.309 2.799 145 Yld 800(2 146 Acryl 1.191 5.190 5.589 2.397 147 Prop 2.004 9.391 6.518 1.958 148 23P .176 3.406 3.821 1.653 149 Acetal 3.119 23.582 57.539 23.005 150 0th 2.316 9.647 .000 .000 151 Unknom 12.777 110.448 114.099 13.084 152 Unacct 78.418 ~61.664 -87.566 57.902 153 00* 2.767 31.564 91.661 50.337 154 002* 2.430 16.635 25.424 7.185 155 A0rPth 3.194 14.581 12.107 4.355 156 AcrlPth 37.271 35 .595 46.164 55 .037 141 Table A.24 - Results for NaOH on the XOC 005 Silica A I I 0 I 0 | E I F I 0 127 REPORT 128 Date 03/30/93 03/30/93 03/30/93 03/30/93 129 Update 04/01/93 04/01/93 04/01/93 04/01/93 130 Cat . ”8011 N801! N80" N80“ 131 T(C) 280.000 300.000 320.000 350.000 132 RT(s) 1.589 1.545 1.512 1.461 133 Err(XC) -8.491 -10.052 1.298 -19.063 134 Conv(80F) 14.902 21.051 23.403 65.804 135 Yld BOF(X) 136 Acryl .534 1.488 3.969 12.304 137 Prop .602 .827 1 .302 3.494 138 23P 1.306 3.446 6.786 9.046 139 Acetal .578 1 .135 3.053 7.390 140 0th . 524 . 000 2 . 249 5 .149 141 Unknown 2.870 3.480 6.864 5.692 142 Unacct 8.488 10.675 -.820 22.730 143 00* .547 1.048 1.510 4.047 144 002* 1.200 3.681 8.398 19.996 145 Yld 800(2) 146 Acryl 3.584 7.071 16.961 18.697 147 Prop 4.038 3.930 5.561 5.310 148 23P 8.761 16.367 28.998 13.746 149 Acetal 3.881 5.390 13.045 11.230 150 0th 3.516 .000 9.609 7.825 151 Unknown 19.260 16.531 29.331 8.650 152 Unacct 56.961 50.710 -3.506 34.542 153 00' 3.669 4.977 6.451 6.150 154 002* 8.056 17.485 35.884 30.387 155 A0rPth 7.621 11.001 22.522 24.008 156 Acr/Pth 47.021 64.275 75.307 77.881 142 Table A.25 - Results for Na3PO4 on the XOC 005 Silica _ A I 8 1 0 1 0 1 E L r 1 0 127 REPORT 128 Date 03/25/93 03/25/93 03/25/93 03/25/93 129 Update 03/25/93 03/25/93 03/25/93 03/25/93 130 Cat. Na3PO4 8a3Po4 8a3Po4 11de 131 1(0) 280.000 300.000 320.000 350.000 132 RT“) 1.987 1.901 1.863 1.784 133 Err(20) 4.982 -24.371 -27.332 -35.850 134 Conv(80F) 7.647 47.708 66.484 90.630 135 Yld 808(2) 136 Acryl 1.407 3.701 8.684 13.978 137 Prop .870 1.255 2.378 5.721 138 23P 4.021 _ 7.161 10.896 7.760 139 Acetal 1.103 2.963 5.134 8.513 140 0th .761 2.325 5.611 6.710 141 Unknown 4.242 5.277 4.058 5.113 142 Unacct -4.757 25.025 29.722 42.836 143 00* .880 1.409 2.997 6.174 144 002* 3.476 7.633 15.590 28.522 145 Yld 800(2) 146 Acryl 18.399 7.757 13.062 15.423 147 Prop 11.383 2.631 3.577 6.312 148 23P 52.581 15.010 16.389 8.562 149 Acetal 14.417 6.211 7.722 9.393 150 0th 9.955 4.874 8.440 7.404 151 Unknown 55.466 11.061 6.103 5.641 152 Unacct -62.201 52.456 44.706 47.265 153 00* 11.501 2.954 4.507 6.813 154 002* 45.459 16.000 23.449 31.471 155 A0rPth 29.783 10.388 16.639 21.735 156 Acr/Pth 61 .779 74.671 78.503 70.957 ._-__..-. -tifi . '1 143 Table A.26 - Results for NaN03 on the XOC 005 Silica _ A I B I C I D I E I F I G 127 REPORT 128 Date 04/08/93 04/08/93 04/08/93 04/08/93 129 Update 04/08/93 04/08/93 04/08/93 04/08/93 130 Cat . "87‘03 118803 1181103 1181103 131 T(C) 280.000 300.000 320.000 350.000 132 RT(8) 2.130 2.082 2.065 1.957 133 End!» -3.815 -6.427 -19.677 ~26.952 134 Conv(BOF) 17.220 37.944 63.942 91.938 135 Yld 80F“) 136 Acryl 1.605 5.307 13.485 22.689 137 Prop .627 .795 .915 1.804 138 23P 5.146 10.914 13.435 12.603 139 Acetal .910 3.765 2.759 9.204 140 0th 1.093 3.246 7.249 7.983 141 Unknown 3.604 5.985 3.148 3.712 142 Unacct 4.236 7.931 22.951 33.944 143 00* .957 1.807 2.297 6.008 144 002* 4.321 12.242 17.757 31.885 145 Yld 80C“) 146 Acryl 9.321 13.988 21.090 24.678 147 Prop 3.640 2.096 1.431 1.962 148 23P 29.882 28.764 21.011 13.708 149 Acetal 5.286 9.923 4.315 10.011 150 0th 6.345 8.555 11.336 8.683 151 Unknown 20.930 15.772 4.924 4.037 152 Unacct 24.596 20.902 35.894 36.921 153 00* 5.555 4.761 3.593 6.535 154 002‘ 25.095 32.262 27.770 34.681 155 A0rPth 12.961 16.084 22.520 26.640 156 Acr/Pth 71.914 86.967 93.648 92.636 144 Table A.27 - Results for NaZHAsO4 on the XOC 005 Silica A I 8 I 0 I 0 I E I P I 0 127 REPORT 128 um 04/01/93 04/01/93 04/01/93 04/01/93 129 Update 04/07/93 04/07/93 04/07/93 04/07/93 130 Cat. 8a28Aao4 8828““ 8112101104 NazuAso4 131 1(0) 280.000 300.000 320.000 350.000 132 81m 2.014 1.965 1.918 1.837 133 Err(20) -21.345 -5.121 -22.626 -21.775 134 0onv(80P) 41.084 44.174 77.041 92.955 135 118 mm 136 Acryl 2.023 6.012 12.917 21.057 137 Prop .826 1.144 1.097 2.042 138 23P 9.235 23.343 18.043 14.275 139 Acetal 1.438 2.638 8.071 11.298 140 0th .647 1.441 7.312 11.191 141 Unknown 3.619 3.375 3.584 5.187 142 Unacct 23.296 6.221 26.017 27.905 143 00* 1.571 1.757 2.517 5.409 144 002* 11.273 16.755 25.648 33.710 145 Yld 800(2) 146 Acryl 4.924 13.609 16.766 22.653 147 Prop 2.011 2.590 1.424 2.196 148 23P 22.480 52.844 23.420 15.357 149 Acetal 3.500 5.971 10.476 12.154 150 0th 1.574 3.262 9.491 12.039 151 Unknown 8.808 7.641 4.653 5.580 152 Unacct 56.704 14.083 33.770 30.020 153 00* 3.825 3.977 3.267 5.819 154 002* 27.438 37.930 33.291 36.265 155 A0rPth 6.935 16.199 18.190 24.849 156 Aer/Pth 71.008 84.013 92.172 91.162 11101110814 $181: UNIV. LIBRRRIES IIIIIWII“IIIUlINHI|1||1|1||||1||I|W" “WNW 31293010373631