ENERGY ENGINEERING

RENEWABLE HYDROGEN PRODUCTION GETS CLEANER WITH UPGRADED 20TH CENTURY CATALYST

By

P.Swathi Priya swathipriya_pedavalli@yahoo.com amruthasudha@yahoo.com Ph 9849322161 Chemical

G.Sudha Rani Chemical

CHEMICAL ENGINEERING DEPT BAPATLA ENGINEERING COLLEGE, BAPATLA

ENERGY ENGINEERING
Renewable hydrogen production gets cleaner with upgraded 20th Century catalyst
P.Swathi Priya,G.Sudharani chemical

Abstract:
Concerns about the depletion of fossil fuel reserves and the pollution caused by continuously increasing energy demands make hydrogen an attractive alternative energy source. Hydrogen is currently derived from nonrenewable natural gas and petroleum, but could in principle be generated from renewable resources such as biomass-derived oxygenated compounds such as ethylene glycol, glycerol, sugars and sugar alcohols or water. Chemical and biological engineers report the discovery of a nickel-tin-aluminium (Raney-NiSn) catalyst that can replace the precious metal platinum in a new, environmentally sustainable, greenhouse-gasneutral, low-temperature, economically viable process yielding fewer contaminants for making hydrogen fuel. Using this catalyst in a single reactor aqueous phase reforming (APR) process, it is possible to generate hydrogen at temperatures near 500 K from biomass instead of 1175 K required with usual processes. This method takes advantage of the unique thermodynamic properties of these oxygenated compounds that allow complete reaction of these compounds with water to H2 and CO2. At these conditions, APR process generates hydrogen without the need to volatilize water, which represents a major energy saving compared to conventional, vapor-phase, steam-reforming processes utilizing non-renewable hydrocarbons. The APR process can be used not only on the small scale to produce fuel for portable devices, but it could also be scaled up as a hydrogen source for industrial applications.

Introduction: Fossil-fuel stocks are a limited resource and, as the worlds governments struggle to agree on a strategy to combat pollution and greenhouse-gas emissions, the search for clean, renewable energy source has never been more intense. Since long the worlds major sources of energy are nonrenewable which include coal, petroleum, gas, nuclear energy. The increasing demand of energy, depleting reserves, pollution strategies necessitate the search for energy through renewable sources such as Solar, Wind, Tidal/Wave, Biomass, Hydroelectric, and Geothermal Energies.

Here we consider the production of a cleaner fuel from renewable biomass-Hydrogen. Changes in global energy production toward a Hydrogen society are predicted to have important economic and environmental benefits because when it burns it combines with oxygen to form water; no toxic byproducts or green house gases are produced. The conventional steam reforming processes for hydrogen production involve the use of nonrenewable sources such as natural gas, naphtha and also high temperatures for the reforming reaction.

As a partial solution to the above problems, we consider the production of hydrogen by a single reactor aqueous-phase reforming process using an upgraded 20th century catalyst.

Process and Experiment: Biomass the product of photosynthesis could become a feed stock of choice for H2 production, even in the absence of environmental premiums. Fractionation of biomass leads to the isolation and depolymerisation of constitutive fractions. And these fractions are further processed to give oxygenated compounds. Glucose is manufactured in vast quantities-for example, in the form of corn syrup from cornstarch, but can also be made from sugar beets, or low cost biomass waste streams like paper mill sludge, cheese whey, corn stover or wood waste. Hydrogenation of
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glucose results in sugar-alcohol sorbitol. Glycerol is a by-product in the production of biodiesel fuel from triglycerides, and glycerol and ethylene glycol can be produced from hydrogenolysis of sorbitol.

We consider production of hydrogen by low-temperature reforming (at 500 K) of oxygenated hydrocarbons having C:O stoichiometry of 1:1. For example, reforming of sugar-alcohol sorbitol to H2 and CO2 occurs according to the following stoichiometric reaction:

C6O6H14(l) + 6H2O(l)

13H2(g) + 6CO2(g)

(1)

The equilibrium constant for reaction (1) per mole of CO2 is of the order of 108 at 500 K, indicating that the conversion of sorbitol in the presence of water to H2 and CO2 is highly favorable. However, the selective generation of hydrogen by this route is difficult because the products H2 and CO2 readily react at low temperatures to form alkanes and water. For example, the equilibrium constant at 500 K for conversion of CO2 and H2 to methane (reaction 2) is of the order 1010 per mole of CO2.

CO2(g) + 4H2(g)

CH4(g) + 2H2O(g)

(2)

Figure 1 shows a schematic representation of the reaction pathways believed to be involved in the formation of H2 and alkanes from oxygenated hydrocarbons over a metal catalyst. The reactant undergoes dehydrogenation steps on the metal surface to give adsorbed intermediates before the cleavage of C-C or C-O bonds. With platinum, the catalyst initially used, the activation energy barriers for cleavage of O-H and C-H bonds are similar; however, Pt-C bonds are more stable than Pt-O bonds, so adsorbed species are probably bonded preferentially to the catalyst surface through Pt-C bonds. Subsequent cleavage of C-C bonds leads to the formation
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of CO and H2, and CO reacts with water to form CO2 and H2 by the water-gas shift reaction (i.e., CO + H2O CO2 + H2).

The further reaction of CO and/or CO2 with H2 leads to alkanes and water by methanation and Fischer-Tropsch reactions; this H2 consuming reaction thus represents a series-selectivity

challenge. In addition, undesirable alkanes can form on the catalyst surface by cleavage of C-O bonds,

followed by hydrogenation of the resulting adsorbed species. This process constitutes a parallel-selectivity challenge. Another pathway that contributes to this parallel-selectivity challenge is cleavage of C-O bonds through dehydration reactions catalyzed by acidic sites associated with the catalyst support or catalyzed by protons in the aqueous solution, followed by hydrogenation reactions on the catalyst. In addition, organic acids can be formed by dehydrogenation reactions catalyzed by the metal, followed by rearrangement reactions that take place in solution or on the catalyst. These organic acids lead to the formation of alkanes from carbon atoms that are not bonded to oxygen atoms.

Table 1 summarizes the experimental results for aqueous-phase reforming of glucose, sorbitol, glycerol, ethylene glycol and methanol. Reactions were carried out over a Pt/Al2O3 catalyst at 498 K and 538 K. The fractions of the feed carbon detected in the effluent gas and liquid streams yield a complete carbon balance for all feed molecules, indicating that negligible amounts of carbon have been deposited on the catalyst. Catalyst performance was stable for long periods of time on stream. The hydrogen selectivities shown in the Table 1 are defined as the number of H2 molecules detected in the effluent gas, normalized by the number of H2
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molecules that would be present if the carbon atoms detected in the effluent gas molecules had all participated in the reforming reaction. Alkane selectivity is defined as the number of carbon atoms in the gaseous alkane products normalized by the total number of carbon atom in the gaseous effluent stream. Figure 2 illustrates that the selectivity for H2 production improves in the order glucose < sorbitol < glycerol < ethylene glycol < methanol. Figure 2 also implies that lower operating temperatures result in higher H2 selectivities, although this trend is in part due to the lower conversions achieved at lower temperatures. The selectivity for alkane production follows a trend with respect to reactant that is opposite to that exhibited by the H2 selectivity.
Fig.2: Comparison of H2 selectivities (%) of Raney-NiSn (squares and circles at 498 and 538 K, respectively) and 3 wt % Pt/Al 2O3 (dashed lines) for aqueous-phase re-forming of 1 wt % oxygenated hydrocarbons versus oxygenated hydrocarbon.

The gas streams from aqueous-phase reforming of the oxygenated hydrocarbons were found to contain low levels of CO (i.e., less than 300 p.p.m). The liquid phase reaction intermediates detected include (in approximate order of decreasing concentration) ethanol, 1,2-propanediol, methanol,1-propanol, acetic acid, ethylene glycol, acetol, 2-propanol, propionic acid, acetone, propionaldehyde, and lactic acid. Analysis of the gas phase effluent indicates the presence of trace amounts of methanol and ethanol (about 300 p.p.m.).High hydrogen yields are only obtained when using sorbitol, glycerol and ethylene glycol as feed molecules for aqueousphase reforming. The lower hydrogen selectivities for the aqueous-phase reforming of glucose, compared to that achieved using the other oxygenated hydrocarbon reactants, are caused at least partially by homogeneous reactions of glucose in the aqueous phase at the temperatures used in this study. However, undesirable homogeneous reactions, as observed with glucose, pose less of a problem when using sorbitol, glycerol,

ethylene glycol and methanol, which makes it possible to generate high yields of hydrogen by the aqueous-phase reforming of more concentrated solutions containing these compounds. For example, it was found that upon increasing the feed concentrations of ethylene glycol or glycerol to 10 wt% (molar ratio H2O/C1=15), it is still possible to achieve high conversions and selectivities for H2 production. (A hydrogen selectivity of 97% was achieved with 62% conversion of 10 wt% ethylene glycol; and a hydrogen selectivity of 70% was achieved with 77% conversion of 10 wt% glycerol) A molar H2O/C1 ratio of 15 is still higher than that typically utilized in conventional vapor-phase reforming of hydrocarbons (molar H2O/C1=3 to 5); but aqueous-phase reforming system has the advantage of not requiring energy-intensive vaporization of water to generate steam.

While the present findings establish that Pt-based catalysts show high activities and good selectivity for the production from sugars and alcohols by aqueous-phase reforming reactions, improvements are necessary to render the process useful. Highly active catalytic materials that can satisfy the series and parallel selectivity challenges, but at lower materials cost than for Pt, are particularly desirable. A good catalyst for production of H2 by aqueous-phase reforming must facilitate C-C bond cleavage and promote removal of adsorbed CO species by the watergas shift reaction, but the catalyst must not facilitate C-O bond cleavage and hydrogenation of CO or CO2. Moreover, new combinations of catalysts and reactor configurations are needed to obtain higher hydrogen yields from more concentrated solutions. Catalysts that exhibit higher activity at lower temperatures, to minimize the deleterious effects of homogeneous decomposition reactions are needed.

Table 1: Experimental data for reforming of oxygenated hydrocarbons:

Conditions Temperature(K) Pressure (bar) %C in liquid phase %C in gas-phase Gas-phase comp.: H2 (mol.%) CO2 (mol.%) CH4 (mol.%) C2H6 (mol.%) C3H8 (mol.%) C4,C5,C6 alkanes %H2 selectivity %Alkane selectivty Glucose 498 29 51 50 51 43 4.0 2.0 0.0 0.0 50 14 538 56 15 84 46 42 7.0 2.7 1.0 1.2 36 33 Sorbitol 498 29(25.8) 39(44) 61(55) 61(59) 35(34) 2.5(6.1) 0.7(0.8) 0.8(0.1) 0.0(0.0) 66(65) 15(19) 538 56(51.4) 12(9) 90(90) 54(52) 36(36) 6.0(8.2) 2.3(2.1) 1.0(0.8) 0.6(0.4) 46(46) 32(31) Glycerol 498 29(25.8) 17(13) 83(86) 64.8(66) 29.7(30) 4.2(4.5) 0.9(0.0) 0.4(0.0) 0.0(0.0) 75(81) 19(13) 538 56(51.4) 2.8(4) 99(100) 57(64) 32(30) 8.3(5.8) 2.0(0.1) 0.7(0.0) 0.0(0.0) 51(76) 31(17) Ethy. Glycol 498 538 29(25.8) 56(51.4) 11(2) 2.9(0) 90(93) 99(100) 70(70) 29.1(28) 0.8(1.3) 0.1(0.0) 0.0(0.0) 0.0(0.0) 96(95) 4(4) 68.7(70) 29(28) 2.0(2.0) 0.3(0.0) 0.0(0.0) 0.0(0.0) 88(95) 8(7.0) Methanol 498 538 29 56 6.5 6.4 94 94 74.6 25 0.4 0.0 0.0 0.0 99 1.7 74.8 24.6 0.6 0.0 0.0 0.0 99 2.7

Reaction kinetics studies for aqueous-phase reforming of ethylene glycol over various supported metals indicate that Pt and Pd catalysts are selected for production of H2, with Pt showing higher catalytic activity. Metals such as Ni and Ru exhibit good catalytic activity but lead to the formation of alkanes, where as Rh, Ir, Co, Cu, Ag, Au and Fe have low catalytic activity for aqueous phase reforming reactions. The high cost and limited availability of Pt makes it advantageous to develop less expensive catalysts for our process based on nonprecious metals. A heterogeneous catalyst was discovered based on Ni, Sn, and Al that is both active and selective for the production of H2 by aqueous-phase reforming of ethylene glycol, glycerol, and sorbitol. This material shows catalytic activity, selectivity, and stability for H2 production that are comparable to the performance of a Pt/Al2O3 catalyst. To aid the search for a non-precious metal catalyst that displays good activity and selectivity for H2 production by aqueous-phase reforming, a high throughput, 48-well parallel batch reactor for catalyst screening was developed. More than 300 catalysts for aqueous-phase reforming of ethylene glycol, including monometallic catalysts, bimetallic catalysts and metallic catalysts promoted with various metal oxides were tested. Promising catalysts from high-through put screening test were subsequently studied in a bench-scale, aqueous-phase reforming flow reactor. Using this approach, it was found that addition of Sn to Raney-Ni catalysts significantly decreased the rate of methane formation without inhibiting the rate of H2 production. The optimal Sn promoted

Raney-Ni catalyst was prepared by decomposition tributyl tin acetate and had a bulk Sn/Ni atomic ratio of 0.075.

Results and discussion: Experimental results for aqueous phase reforming of sorbitol, glycerol and ethylene glycol over Raney-NiSn catalyst were shown in Table 1(in braces).The gas-phase products were 50 t0 70 mol% H2, 30 to 40 mole% CO2, 2 to 11 mole% alkanes. Small amounts of CO were detected in the outlet gas stream. The liquid products contained small amounts of alcohols, organic acids, and aldehydes (<50 p.p.m. at conversions of >90%), as determined by high-performance liquid chromatography and gas chromatography. Analysis of effluent gas liquid streams yielded a complete carbon balance for all feed molecules. The selectivity for production of H2 decreased slightly as the concentration of the oxygenated hydrocarbons increased from 1 to 5 wt%. Catalytic activity measured at 498 K and conversions near 15% decreased by only 15% after 10 hours and reached a constant value equal to 72% of the initial activity after 48 hours. Selectivities for production of H2 and alkanes are shown vs the feed molecule and temperature in figure 2 for the Raney-NiSn and 3 wt% Pt/Al2O3 catalysts.

The Raney-NiSn catalyst exhibited higher selectivity for production of alkanes than Pt/Al2O3 for reforming of glycerol and ethylene glycol solutions, especially at higher temperatures. Comparable selectivities were observed over the two catalysts when sorbitol was used as the feed molecule. The CO concentrations of the product gases for both catalysts were also comparable (100 to 1000 p.p.m.). Over both catalysts, selectivity for production of H2 improves in the order sorbitol<glycerol<ethylene glycol, whereas the selectivity for production of alkanes follows the opposite trend. Lower operating temperatures resulted in higher selectivities for production of H2 (fig. 2), which may be due in part to lower conversions of feed molecules. The beneficial effect of Sn on the selectivity for production of H2 may be caused by
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the presence of Sn at Ni defect sites (and by the formation of Ni-Sn alloy surfaces, such as Ni3Sn alloy) where the methane formation reaction preferentially takes place. The decoration of defect sites by Sn may thereby suppress methanation reactions.

Conclusions: 1. Raney-NiSn catalyst proved to be effective at separating hydrogen from

biomass derived molecules with reduced production of alkanes (series and parallel selectivity challenge) and instead generating more hydrogen. 2. The relative activity of the Raney-NiSn catalyst even at low temperatures,

minimizes the deleterious effects of homogeneous decomposition reactions in more concentrated solutions. 3. Low CO in gas-phase effluent states the process relatively Eco-friendly.

References: 1. R.D.Cortright, R.R.Davda, J.A.Dumesic, Nature 418, 964 (2002). 2. G.W.Huber, J.W.Shabaker, J.A.Dumesic, Science 300, 2075 (2003). 3. P.Gallezot, N.Nicolaus, G.Fleche, P.Fuetes, A.Perrard, J. Catal. 180, 51 (1998). 4. F.Ma, M.A.Hanna, Bioresource Technol. 70, 1 (1999). 5. E.Tronconi et al., Chem. Eng. Sci. 47, 2451 (1992). 6. J.R.Rostrup-Nielsen, Phy.Chem.Chem.Phy. 3, 283 (2001).

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