Groundwater Quality: Remediation and Protection (Proceedings of the GQ'98 Conference held at Tubingen, Germany, September 1998).

IAHS Publ. no. 250, 1998.

491

Catalytic dechlorination of halogenated hydrocarbon compounds using supported palladium: a preliminary assessment of matrix effects
NAOKO MUNAKATA, PAUL V. ROBERTS, MARTIN REINHARD
Department of Civil and Environmental Engineering, Stanford University, Stanford, California 94305-4020, USA

WALT W. McNAB
Lawrence Livermore National Laboratory, Livermore, California 94550, USA

Abstract Previous studies indicate that the hydrodehalogenation of halogenated hydrocarbons by supported Pd and H2 may be a promising technology for remediating contaminated waters. Bench-scale laboratory studies have demonstrated the technical feasibility of trichloroethylene (TCE) reduction to ethane by hydrogen in a Pd-catalysed hydrodehalogenation reaction under ideal conditions. This study investigated catalyst activity in bench-scale continuous-flow columns under a variety of water matrices. Deionized (DI) water caused no observable deactivation, and phosphate caused minimal deactivation when added to DI water. Nitrate, which was amended to DI water, competed with TCE for hydrogen or catalyst sites but caused no deactivation. Carbonate, carbon dioxide and groundwater from Livermore, California, all caused gradual deactivation of the palladium. Regeneration of the carbonate-deactivated catalyst through evacuation and oxidation improved catalyst activity.

INTRODUCTION Widespread contamination of groundwaters by halogenated solvents and pesticides has resulted in the need for effective water treatment methods. Conventional technologies such as granular activated carbon (GAC) adsorption simply transfer contaminants from one medium to another, thus requiring additional incineration or regeneration, both of which are expensive. As a result, methods which eliminate, rather than transfer, pollutants are preferable. Previous studies have indicated that reduction by hydrogen in a Pd-catalysed hydrodehalogenation reaction may be one such promising method. Recent batch experiments showed rapid and fairly complete ( > 9 9 % ) removal of compounds such as trichloroethylene (TCE) and l,2-dibromo-3chloropropane (DBCP) from de-ionized (DI) water (Schreier & Reinhard, 1995; Siantar et al., 1996) In this work, Pd catalyst deactivation is examined in column systems with various water matrices (DI water, solutions of known additions, and complex natural groundwaters), with the objective of defining reaction competitors, catalyst poisons, and potential pre-treatment or regeneration needs. Catalyst deactivation is generally

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defined as a reduction in the ability of a catalyst to transform a given substrate (activity) or to transform a given substrate to a desired product (selectivity). Catalyst deactivation can occur by the irreversible adsorption or reaction of a substrate onto the active metal sites (poisoning), poison-induced restructuring of the metal surface, or by pore plugging/coating (Hughes, 1984). Although several compounds such as sulphide are well-known palladium catalyst poisons (Rylander, 1985), there are no proven methods for predicting which, if any, natural groundwater solutes will cause problems for a given reaction under specified conditions. Many potential competitors and poisons may be found as natural solutes including, nitrate, sulphate, carbonate, chromate, phosphate, various metals, dissolved oxygen, and dissolved organic matter. Precipitation of calcium and magnesium carbonates may lead to pore plugging or coating as many natural waters are saturated with these salts. Chromate species may also lead to pore plugging or coating if they are reduced in the system as the reduced forms are less soluble than the oxidized forms. The transformation of TCE by a column of Pd/Al203 catalyst was tested using groundwater from the Livermore groundwater basin, DI water and DI water spiked with different anions encountered in groundwater. Furthermore, an effort was made to evaluate the potential for regenerating deactivated catalyst.

MATERIALS AND METHODS Experimental apparatus Columns were constructed of 0.7 cm ID glass tubing, filled with Pd/Al203 catalyst (UOP) and crushed to a 20-50 mesh (0.3-0.8 mm) size fraction. The catalyst has a measured composition of approximately 1 % Pd by weight. The catalyst mass in each column ranges from 0.1-2.0 g. The flow system (Fig. 1) consists of a 11 or 18.5 litre reservoir of water, purged with pure H2 gas for at least 30 min. Hydrogen pressure (115-156 kPa) Water H,

OUT 1.5 atm H, Water

Fig. 1 Column experimental set-up.

Pd catalyst column IN

Catalytic dechlorination of halogenated hydrocarbon compounds using supported palladium 493 Table 1 Livermore water quality data, all values (except pH) in mg l"1. Component Carbonate Nitrate Sulphate Chloride Ca2+ Mg2+ K+ Na+ pH 180 23 8.2 33 39 12 1.8 35 TA-

pneumatically drives the water from the reservoir to a T-joint, where a saturated solution of TCE is added using a syringe pump. The combined stream then flows through the catalyst column; valves allow the collection of column inlet and outlet samples. Both the water and TCE flow rates can be varied, thus making the feed concentration and the column residence time adjustable. In these experiments, the water flow rate was 1-9 ml min1 and the inlet TCE concentration was varied between zero and 49 mg r1. In each experiment, the reservoir was filled with DI water or groundwater from Livermore, California (water quality data provided in Table 1). In several runs, the water was amended with nitrate, phosphate, carbonate or C0 2 . Carbonate and phosphate were added directly to the reservoir water in the form of sodium carbonate or a 50/50 mixture of mono- and di-basic potassium phosphate. Nitrate was added with a syringe feed to a DI column flow from the reservoir. In two separate tests, C0 2 was added to DI and groundwater by purging with a 90% H2/10% C0 2 gas mixture (C02 partial pressure of approximately 13.8 kPa), rather than pure H2. The conditions for each experiment are summarized in Table 2. Analytical methods Inlet and outlet TCE concentrations were measured using headspace samples in an ECD detector on the Hewlett Packard 5890 Series II Gas Chromatograph. Inlet and outlet nitrate concentrations were measured using a Hewlett Packard 8451A Diode Array Spectrophotometer at a UV absorbence of 210 nm. Aqueous palladium was determined using a Varian SpectrAA 640 atomic absorption analyser with a GTA 100 graphite furnace analyser. Absorption at
Table 2 Experimental conditions. System parameters DI water DI water + phosphate DI water + carbonate DI water + C0 2 Groundwater Groundwater + CO, Catalyst mass (g) 2.0 0.301 0.100 0.100 0.300 0.101 Column volume (ml) 3.85 0.69 0.23 0.23 0.58 0.23 H2 pressure (kPa) 125 156 150 156 156 156 Flow rates (ml min"1) 1.0-9.0 0.90-1.10 1.00-1.20 0.5-5.5 0.85-1.10 1.0 TCE cone. (mg I"1) 0.4-49 0.4-8.0 2-7 0.5-1.5 1-6 3-19

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244.8 nm from a palladium lamp was measured and calibrated against prepared ammonium chloropalladate standards. The detection limit of the instrument is approximately 2 u.g l"1; column effluent samples were concentrated 25 times using a Brinkman Buchi Rotoevaporator before being measured. All standards and samples were acidified with nitric acid to a pH of 2. Catalyst dissolution studies were conducted in batch reactors. A total of 10 mg of palladium was added to 20 ml of nitric acid solutions ranging in pH from 0.85 to 4.5. The samples were shaken for 2 h and allowed to equilibrate for 20 h before being measured using the AA spectrophotometer. RESULTS AND DISCUSSION De-ionized water and nitrate In the baseline column test with DI water, inlet TCE concentrations between 1.5 mg l"1 and 25 mg l"1 were more than 99% transformed, with no noticeable decrease in catalyst activity over 5 months (data not shown). TCE concentrations above 30 mg l"1 exceeded the stoichiometric TCE:H2 ratio for the complete reduction of TCE to ethane. The degradation rate fell, indicating complete usage of the available hydrogen (approx. 2 mg H2 per litre). When nitrate was added to the system, it appeared to compete with the TCE for hydrogen and/or catalyst sites. As the inlet nitrate concentration was increased, the ability of the system to reduce TCE decreased. For example, in the absence of nitrate, TCE was 99.97% reduced, from 25 mg l"1 to 8.2 u.g l"1. At a nitrate concentration of 44 mg l"1 nitrate, TCE was reduced only 52%, from 6 to 2.9 mg 1"'. When nitrate addition was stopped, the column returned to its original TCE removal capacity.

Phosphate To investigate the effects of phosphate on the catalyst life, 100 mg l"1 of phosphate (50 mg phosphate per litre each of mono- and di-basic potassium phosphate) was added to the reservoir DI water. This addition appeared to cause minor deactivation of the catalyst (data not shown). Further tests are being conducted to verify the phosphate effects.

Carbonate species Experiments with the Livermore groundwater and the C0 2 - and Na2C03-amended waters yielded transformation of TCE but showed deactivation of the catalyst. C02-amended DI water completely deactivated the catalyst in 13 days, while the DI water alone showed no deactivation after 5 months. Similarly, in the groundwater test, the C02-amended water deactivated the catalyst more rapidly than the water alone (Fig. 2).

Catalytic dechlorination of halogenated hydrocarbon compounds using supported palladium 495 100.00% 90.00% 80.00% 70.00% 60.00% 50.00% 40.00% 30.00% 20.00% 10.00% 0.00% O.i
&

~ Groundwater alone Groundwater + CO,

10.00

20.00

25.00

30.00

Run Time (days) Fig. 2 Deactivation of the catalyst by groundwater and by C0 2 amended groundwater.

In the Na2C03-amended DI water (500 mg l"1 Na2C03), TCE conversion decreased to 17.5% after 5.5 days, or 130 h (data not shown). An initial attempt was made to regenerate the catalyst by flushing the column with DI water under normal experimental conditions: 152 kPa of H2 pressure in the water reservoir, and TCE feed via a syringe pump. This resulted in(an increase in conversion from 5% to 20% (data not shown). The literature suggests that a carbonate species (such as carbonate, carbonic acid and carbon dioxide) can sorb to the catalyst surface and be reduced to CO, which can poison Pd (Kramer et al., 1995). Based on successful regeneration techniques described in the literature, the deactivated catalyst was placed under 0.07 mm Hg vacuum at 300C for 2.0 min, then under oxygen flow at 300C for 15 min (Doering et al, 1980). During the regeneration process, approximately 25% of the catalyst mass was lost. When the column was restarted on the DI water flow, the catalyst showed virtually complete recovery of activity, given the mass lost. However, it was difficult to fully evaluate catalyst regeneration from this test, due to the fluctuating performance of the column.

Effect of pH on palladium dissolution In the DI water column, atomic absorption spectrophotometry showed traces of palladium dissolution when TCE was present in the influent stream, but not in DI water alone. This finding led to the hypothesis that the dissolution may be caused by localized regions of low pH formed by hydronium ions produced from the hydrodehalogenation reaction. Batch experiments to study the effects of pH on catalyst dissolution were performed by placing catalyst beads in nitric acid solutions of pH between 1 and 4.5, and measuring the Pd concentration at the various pH values. The results (not shown) indicate that reactor conditions should be kept above a pH of approximately 4 (below that point, Pd dissolution increases significantly).

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SUMMARY The supported Pd/H2 system, with its ability to reduce TCE to ethane without significant by-product formation, has great potential as an alternative remediation technology. The results shown here demonstrate that the use of such a system to remove TCE from relatively clean water is technically feasible. However, it is also clear that some components likely to be present in a groundwater matrix, such as carbonate species, can have a detrimental effect on the catalyst activity and the hydrodehalogenation reaction. Future work will focus on understanding these effects and mitigating them through regeneration, pre-treatment and manipulation of the Pd catalyst.

REFERENCES
Doering, D. L., Poppa, H. & Dickinson, J. T. (1980) Changes induced on the surfaces of small Pd clusters by the thermal desorption of CO. J. Vacuum Science and Technology 17, 198-200. Hughes, R. (1984) Deactivation of Catalysts. Academic Press, London, UK. Kramer, H., Levy, M. & Warshawsky, A. (1995) Hydrogen storage by the bicarbonate/formate reaction. Studies on the activity of Pd catalysts. Int. J. Hydrogen Energy 20, 229-233. Rylander, P. N. (1985) Hydrognation Methods. Academic Press, New York, USA. Schreier, C. G. & Reinhard, M. (1995) Catalytic hydrodehalogenation of chlorinated ethylenes using palladium and hydrogen for the treatment of contaminated water. Chemosphere 31, 3475-3487. Siantar, D., Schreier, C. G., Chou, C.-S. & Reinhard, M. (1996) Treatment of l,2-dibromo-3-chloropropane and nitrate-contaminated water with zero-valent iron or hydrogen/palladium catalysts. Wat. Res. 30, 2315-2322.