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HYDROGEN PRODUCTION BY AUTOTHERMAL REFORMING OF ETHANOL PILOT PLANT

ANTONIO JOS MARIN NETO (1) JOO CARLOS CAMARGO (1) DANIEL GABRIEL LOPES (1) NEWTON PIMENTA NEVES JR. (2) EDGAR A. DE GODOI RODRIGUES PINTO (2) ENNIO PERES DA SILVA (2) ANDR LUIS FURLAN (3) PAULO F. P. FERREIRA (1)
(2)

Hytron Hydrogen Technology, Campinas/SP, Brazil Hydrogen Laboratory Applied Physics Dept IFGW - Unicamp, Campinas/SP (3) Faculdade de Engenharia Mecnica Unicamp, Campinas/SP

(1)

ABSTRACT
This work provides information about the development of an integrated unit for hydrogen production by autothermal reforming of ethanol with nominal capacity of 1 kg/h H2 4.5 (99.995%). The unit is composed by a Fuel Processing Module (FPM), resulting from autothermal and shift reactor integration, responsible for the thermochemical step, plus an overheater of the liquid input (EtOH and H2O), operated recovering thermal energy from PSA blown-down (H2 Purification Module - MPH2), besides other thermal equipment which completes the integration. Using a computational routine for scaling the process and preliminary performance analysis, it was possible to optimize operating conditions, essential along unit operations design. Likewise, performance estimation of the integrated unit proceeds, which shows efficiency about 72.5% from FPM. Coupled with the PSA recovery rate, 72.7%, the unit could achieve overall energy performance of 52.7%, or 74.4% working in co-generation of hydrogen and heat.

KEY WORDS
Autothermal Reforming; Ethanol; PSA; Pilot Plant.

1. INTRODUCTION
Hydrogen is currently associated to many industrialized products, which demand it in their production. Metallurgical applications (reduction, annealing), hydrogenation of oils and fats in chemical and food industries, glass production, chemical specialties applied in medicines and cosmetics (hydrogen peroxide, mannitol - sorbitol), aerospace fuel appliances, coolant in large scale electric generators, fertilizers, polymers, centralized power generation (heat and electricity) and, more recently, decentralized power generation using ICEs, microturbines and fuel cells, are remarket applications of hydrogen. The current Brazilian hydrogen production matrix, plus its future demand in energy applications (gas stations, distributed generation sites), justify the development of plants up to 30 kg/h of H2,
1 Correspondence should be addressed to Antonio Marin: Phone: +55 (19) 3032-2522; e-mail: antonio@hytron.com.br

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exploring advantages such as the use of local fuel resources. This is the case of consolidated distribution fuels, such as ethanol, including, in the math of its use, the techno-economic attractiveness of the Brazilian fuel and its environmental advantages.

2. OBJECTIVES
This work reports the current development stage of a pilot plant intended to produce hydrogen through autothermal reforming of ethanol. The FPM is integrated to a PSA (Pressure Swing Adsorption) module in order to purify hydrogen present in the FPM outlet gas stream, plant with nominal production rate of 1 kg/h H2 (4.5). This industrial development is supported by FAPESP through the second phase of PIPE program (Technological Innovation in Small Businesses Program). Other objectives of this project includes the unit performance evaluation under continuous and discontinuous schedule, in order to obtain essential market parameters such as availability and reliability factor, as well the maintenance schedule of the system.

3. METHODOLOGY
The present development includes conceptual project, construction, assembly, commissioning and operation of an ethanol autothermal reformer integrated to a PSA in order to produce pure hydrogen. This configuration allows, through operational parameters adjustments, distinct grades hydrogen production, making the plant able to meet energetic and industrial applications of this gas. The FPM, reformer itself, is composed by an autothermal reforming reactor, an intermediate temperature shift reactor (ITSR), an overheater of the liquid input, and heat exchangers, finalizing systems thermal integration. A seven-bed PSA module is responsible for hydrogen purification, while other balance equipments are responsible for filtering, drying and gas pressure controlling coming from both modules of the unit. The plant is overseen by a PLC (Programmable Logic Controller) which is also the interface for operators and remote equipments alike. Theoretical basis results of constant improvement, carried out in several demonstration projects exploring thermochemical processes for hydrogen production. The pilot plant demonstration will contribute to model improvement, with theoretical reformulations and refinement of empirical parameters from experimental expertise acquired by the project team.

3.1 FUEL PROCESSING MODULE (FPM) FPM is designed by integration of two catalytic reactors, autothermal reforming reactor (ATR) and intermediate temperature shift reactor (ITSR). Besides these, FPM makes up a thermal bed for inputs (ethanol and water) overheating, while energy is recovered by oxidation of the lean gas blown-down from PSA.
The software EES (Engineering Equation Solver, f-chart) was used to solve the thermodynamic problem of gas composition determination, supported by specific boundary condition of each process equipment. The final integration, system studied for performance analysis, after performance analysis of unit operations individually, is shown in Figure 1.

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Air

SH

ATR
HX#1

Air

Raffinate

LTS
Vent

EtOH

HX#2 H2, N2, CO2

H 2O

Water
JT

Adsorption Dryer Refrigeration Dryer

PSA
Ethanol Hydrogen Water Air Ethanol/water N2, CO2 , H2O (Exaust)

Ethanol Autothermal Reforming System

H2 , CO2, N2 (Syngas) Raffinate R-134a

Figure 1. Process Flow Diagram considered in FPM performance analysis.

3.1.1 AUTOTHERMAL REFORMING REACTOR (ATR) The concept explored in the present pilot plant is the autothermal reformation, denomination of the process in which the reactions of reforming and partial oxidation occurs in the same bed, resulting in a thermal stability related to the coupling of the named reactions.
The condition indicates that the amount of energy generated inside the reactor is balanced by the amount of energy demanded by reformation of the non-oxidized fuel fraction, plus thermal losses of the process to environment, resulting in a constant temperature condition. Once the generation and energy demand are confined, the load response is optimized, enabling improved downstream integration. Experimental verification of many chemical species derived from reforming process shows complexity when such process is described. The direct implication is the inexistence of a single global reaction, especially because these species are closely related to the thermodynamic condition of the ATR. This is a complex behavior explored during performance evaluation through chemical equilibrium analysis. Such analysis considered the fact that a system is in thermodynamic equilibrium when positioned over the free energy minimum, depending on systems independent variables (pressure and stoichiometry of the process - O2/Fuel and H2O/Fuel), and neutral mass balance. This analysis can be described by equations (01) and (02), below:

G o + RT ln fi i = 1,2,..., N .

i i P
Po

+ k ai ,k = 0;
k

(01)

n b
i

i i ,k

= Bk ;
(02)

k = 1,2,..., w
Where:

G fi: Free Energy of Formation of the Chemical Specie i; R: Gas Universal Constant;

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T: Temperature; i: Molar Fraction of the Chemical Specie i; i: Fugacity Coeficient of the Chemical Specie i in Solution; P: Operating Pressure; o P : Standard Pressure; k: Lagrange Multiplier to the Chemical Element k; ai,k: Multiplicity of the Chemical Element k in Chemical Specie i; bi,k: Multiplicity of the Chemical Element k in Chemical Specie i; ni: Mol Number of the Chemical Specie i; Bk: Mol Number of the Chemical Element k; w: Total Number of Chemical Elements Involved in the Process. The understanding of the autothermal reforming of any hydrocarbon, alcoholic or not, is similar to the concept of adiabatic flame temperature. The ATR temperature is precisely determined by O2/Fuel and H2O/Fuel ratios, as well the gas composition from such partial oxidation, since there is no availability of oxidizing agent to drive all the fuel input to oxidation overall products, CO2 and H2O, and the oxidized fraction of the fuel is responsible to provide heat for reformation of the non-oxidized fraction. It results that the ATR bed temperature is not an independent parameter but a result of input process stoichiometry and its thermal condition. The only temperature that can be imposed, with limitations oriented by the context of this integrated system, is the ATRs reactants temperature of injection. To reach a given temperature in ATR bed, the lower is the amount of energy required, or similarly, lower is the amount the of the oxidizing agent, how much higher was the reactants input temperature, since lower heat is required to achieve the desired thermal condition (and less fuel consumed to this). By association, it can be expected to be lesser the air demand in the proposed case, how much higher was the reactants injection temperature at ATR. Thus, the set of independent variables, or the process boundary conditions, includes: ATRs reactants injection temperature (Tinj), operating pressure (Pop), O2/Fuel and H2O/Fuel.

3.1.2 INTERMEDIATE TEMPERATURE SHIFT REACTOR (ITSR) The work reaction in ITSR is represented by equation (03). This is a simple exchange reaction between carbon monoxide (CO) and water, producing carbon dioxide (CO2) and additional hydrogen, reaction slightly exothermic and whose exothermic nature decreases increasing process temperature.

CO + H 2O H 2 + CO2

(03)

Equation (03) can be written as (04), where ni represents the stoichiometry coefficient of specie i:

nCOCO + n H 2O H 2O n H 2 H 2 + nCO 2CO2

(04)

The transformation is fully known and the conversion is connected to thermodynamic condition of the process and its influence on the reaction equilibrium. This dependence is expressed by the set of equations (05):

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((nCO )(nH 2O )).K j = ((nCO 2 + )(nH 2 + )); . .

G o j K j exp RT ; o CO 2 H2 CO H2 G j = ((nCO 2 .GLTS ) + (nH 2 .GLTS )) ((nCO .GLTS ) + (nH 2O .GLTSO ))
In (05): ni: Stoichiometry Coefficient of the Chemical Specie i; : Reaction Coordinate; Kj: Equilibrium Constant of the Reaction j; o G j: Free Energy Variation of the Reaction j.

(05)

3.1.3 ENERGY EFFICIENCY ANALYSIS It was considered the energy efficiency of the thermochemical process through direct association of two catalytic reactors (ATR + ITSR), based on LHV's of interesting chemical species. Thus, the efficiency of the ATR reactor took into account the LHV's of H2 and CO, since CO is converted into CO2 and H2 downstream in ITSR, which is expressed in equation (06):

ATR =

(n.LHV ) H 2 + (n.LHV ) CO (n.LHV ) EtOH (n.LHV ) H 2 (n.LHV ) EtOH

(06)
ATR

Likewise, for ITSR:

ITSR =

(07)
ITSR

In (06) e (07):

x: Energy Efficiency of the Reactor x; n: Mol Number; LHV: Lower Heating Value.
3.2 H2 PURIFICATION MODULE (MPH2) PSA process explores the interaction of the crystalline structures of some natural or synthetic materials, commonly known as molecular sieves, with the electric dipole moment of liquid or gaseous substances, which is called physisorption. Often, molecules with higher affinity to crystalline structures can move lower affinity ones, which denote the selectivity of different molecular sieves promoting specific separations.
Among molecular sieves, porous crystalline zeolites, aluminosilicates with high surface areas. Such structures are formed by tetrahedral (AlO4) and (SiO4), basic cells of various types of zeolites, such as types A and X, commercially well known [1]. Due to the presence of alumina, the zeolites exhibit intense electrostatic fields counterbalanced by cations that are added to them. Such cations are chosen so that the pore size (or arrangement of the crystal structure) and the intensity of electric fields are precisely determined, reaching specific characteristics of adsorption. High pressures and/or the low temperatures provide greater affinity between the gas phase and the adsorber (solid fixed phase), while opposite situations determine accurately the condition of reversibility.

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MPH2 is composed by 07 layered columns. The first layer of each bed is filled with granular activated carbon with the primary purpose of CO2 removing from the gas stream. Next layer, MS-5A, is oriented for other chemical species removal from reformate. Besides fast cycles of operation, as objectified, the final size of the purification bed is determined by N2, due to small interaction between this specie and assumed higher adsorption capacity zeolite, as can be observed in Figure 2, illustrating the performance of the molecular sieves used and the chemical species involved. The MPH2 has layout and operational logic described in Figure 3.

CA BPL @ 30 C
9 8 7 6 mmole/g 5 4 3 2 1 0 1 2 3 4 5 atm 10 15 20 25

f(H2) f(N2) f(CO) f(CH4) f(CO2)

MS-5A @ 30 C
5 4.5 4 3.5 mmole/g 3 2.5 2 1.5 1 0.5 0 1 2 3 4 5 atm 10 15 20 25 f(H2) f(N2) f(CH4) f(CO) f(CO2)

Figure 2. Performance of sorbents used in MPH2.

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Bed 1 01 02 03 04 05 06 07 E1P E3P D E3D E1D PF E2P P PP E2D A E1P E3P D E3D E1D PF E2P P PP E2D E1P E3P D E3D PF E2P P PP E1P E3P D PF E2P P E1P E3P PF E2P E1P PF 2 3 A 4 5 6 7 E1D A 8 9 10 E3D E1D A 11 12 13 D E3D E1D A 14 15 P PP E2D 16 E3P D E3D E1D A 17 18 19 E1P E3P D E3D E1D A A 20 21 Time Unit

E2D

PP E2D

E2P P PP E2D

PF E2P P PP E2D

A EnP EnD PP P D PF

Adsorption n-th Equalization (Pressurization) n-th Equalization (Depressurization) Providing Purge Purge Blown-down Final Pressurization

Retention of the species with higher adsorbent affinity (High pressures and Low temperature) Product recovery through sequential bed pressurization Sequential bed depressurization in order to recovery product Product disposal in order to clean interstitial and bulk spaces of the molecular sieves Interstitial clean-up of the bed for regeneration Depressurization for regeneration Final pressurization with clean product

Figure 3. Operation logic and topology proposed for MPH2. As can be seen from Figure 3, the 07 columns system provides three equalizations (sequential depressurization that results in H2 recovery withdrawal adsorption stage and gradual pressurization of the columns coming from regeneration by total depressurization) before blowndown of the column, producing fuel gas for thermal recovery in the overheater. The purification column performance is defined in terms of its Recovery Index (RI), ratio between the sum of purified H2 by the considered column (in adsorption and consecutive equalization stages), and the total amount of H2 determined to the purification process.

4. RESULTS
4.1 FUEL PROCESSING MODULE (FPM) The preliminary data related to energetic performance of the thermochemical process is shown in Figure 4, for the independent variables listed above.

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Figure 4. Ethanol autothermal reforming - energy performance.

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The graphs presented in Figure 4 reveal important aspects of the autothermal reforming process. The increase in operating pressure shifts the maximum energetic efficiencies for higher O2/Fuel ratios, which is related to the enthalpies behavior of the of the steam reforming and partial oxidation processes, simultaneous in ATR. Furthermore, the increase in pressure causes absolute term reduction of the maximum thermodynamic efficiency achieved by the process. Illustratively, if ATRs reactants injection temperature is kept at 450 the ATR efficiency de creases 6.7% between 2-20 bar (4.6% C, between 2-10 bar), within the same ranges of input stoichiometry. The injection temperature has a direct contribution to the energy behavior of the process, shifting the maximum thermodynamic efficiency for smaller O2/Fuel ratios, as expected. Therefore, increasing this process parameter, higher absolute efficiencies are reached for autothermal reforming, increasing 1.5% between 300 - 450C, and 3.9% between 300 600C, for constant pressure at 10 bar. This behavior is expressed in Figure 5.
Energy Efficiency - ATR
0.95 2 bar 10 bar 20 bar

0.9

0.85

0.8

0.75

0.7 300 450 T inj ( C) 600

(a)
Energy Efficiency - ATR+ITSR
0.95 2 bar 10 bar 20 bar

0.9

0.85

0.8

0.75

0.7 300 450 T inj ( C) 600

(b) Figure 5. Energy performance of ATR and ATR + ITSR association. The results of Figure 5 were obtained considering the condition of maximum efficiency, according to the equations (06) and (07), for each fixed parameter, operating pressure and injection temperature, determining the Air/EtOH and H2O/EtOH ratios under distinct injection temperatures and operating pressures. The input stoichiometry of the process, expressed in Figure 5, is in accordance with Table 1.

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Table 1. Input stoichiometric in the ethanol reforming process, based on maximization of the process energy efficiency. ATR ATR + ITSR Air/EtOH Air/EtOH P (bar) Tinj ( C) H2O/EtOH H2O/EtOH 2 300 4 0 4 5.4 450 4 0 3.4 7.5 600 3 7 2.8 7.5 10 300 4.5 0 4.6 4.1 450 4.5 0 4.2 6.8 600 4 1 3.5 7.5 20 300 5 0 4.9 3.6 450 4.5 0 4.5 5.2 600 4.5 0 3.9 7.5 In such approach, from the point of view of the integrated unit, and in accordance with the earlier assumptions, the increase in energy efficiency denotes higher molar fractions of H2 in the final reformate, which also provides a better performance for PSA (in terms of its RI), and higher overall performance indicated by the relative increase due solely to thermochemical step. In all cases, the efficiency of ATR + ITSR integration is smaller than the indicated performance of the ATR, as expected, which is due to non-isentropic nature of the process. At 450C, considered rated injection temperature, the pressure variation between 2-10 bar decreases the maximum thermodynamic efficiency of the process in 8.0% (11.4% between 2-20 bar). Again, increasing injection temperature (and process at 10 bar), there is a gain estimated in 4.4% given by the increase in injection temperature from 300 - 450C, and additional 10.3% between 300 - 600C. The increase in the injection temperature also shifts the maximum efficiency of the association ATR + ITSR for higher H2O/Fuel ratios, which is related to the fact that these higher temperatures shift the chemical equilibrium of the ATR in the direction of greater CO content, implying greater mole fraction of water demanded for maintenance of the conversions associated with the reactor ITSR. These results were not related to the complete thermal integration of the system, and the fact that higher levels of water added as an input of ATR represents greater energy expended in phase changing and superstoichiometric overheated steam. Though it maintains the function of shifting the chemical equilibrium in order to avoid the formation of unwanted by-products (such as C) also represents thermal load to heat exchangers (including overheater) and reason for catalytic beds oversizing, which also falls financially over the unit. Refinements of these calculations should include this consideration and the fact that the maximum overheating is related to the lean gas use, rejected by MPH2. Its denotes a noble, and necessary, disposal of combustible gases from the non-ideal recovery of the MPH2. The PSA performance is closely related to the performance of the reformer itself, once higher H2 mole fraction reformate determines higher RI's, and consequently, lower thermal potential in the PSA blown-down, therefore less capacity to overheating the ATR inputs which leads to lower mole fraction of H2 due to this (an inverse non-linear interdependence). Among the considerations taken was determined, as a condition for safe ATR operation (a condition associated with the surroundings of maximum efficiency of the association ATR + ITSR) the O2/Fuel = 0.8 (Air/Fuel = 3.81) and H2O/Fuel = 3.81 ratios. This results a reformate from the ATR catalytic bed according to Table 2.

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Table 2. Reformate from ATR O2/Fuel =0.8 and H2O/Fuel = 3.81. Reactants Injection Temperature = 450C. P = 1200 kPa. Species (mol/mol) H 2O 0,2969 H2 0,2713 N2 0,2592 CO 0,0700 CO2 0,0930 CH4 0,0094 According to calculations, besides the excess water for the process involves a larger ATR catalyst bed, the mole fraction becomes negligible for the by-products of nature C2, C3+ and C. The reforming gas leaves this reactor with temperature about 770C, inlet temperature of the heat exchanger 1 (HX#1 - ATR-ITSR). Avoiding the formation of higher hydrocarbons is possible to ensure experimental results near to the thermodynamic calculations, particularly related to ethylene (C2H4), chemical specie responsible for most of the C(s) formation through its thermal degradation, which leads to deactivation of catalysts by impregnation and loss of active area. The HX#1 does not change the composition of the reformate and reduces its temperature to a nominal value of 350 It should be emphasized tha t the optimum temperature designed for C. the reactor ITSR provides a inlet condition of 300C, which is in agreement with the experimental performance of the catalyst [2]. As a way to add one degree of freedom to operation control of ITSR, its inlet temperature has the difference (350-300) adjusted with additional water injection, which promotes not only C sought adequacy, but also a superstoichiometric fraction of water in gas phase, which shifts the equilibrium conversion of ITSR towards lower mole fractions of CO. This strategy seeks to address different temperatures output of HX#1, because of their innovative geometry, which brings greater uncertainty regarding its performance deviation from the rated design, especially for partial loads of the pilot plant. The ITSR catalytic bed receives reformate described in Table 2 at 300C, changing its composition in agreement with Table 3. Table 3. Reformate from ITSR. Tin = 300 and T out = 366C, P = 1170 kPa. C Species (mol/mol) H 2O 0,2621 H2 0,3198 N2 0,2509 CO 0,0107 CO2 0,1471 CH4 0,0091 The higher ITSR output temperature (366C) plays the exothermic nature of the process. At this point the gas covers the second heat exchanger (HX#2), which cools it while heats up the mixture of liquid chemicals of the process (EtOH + H2O), operating as a pre-condenser for the stream from ITSR. HX#2 output reformate has its temperature calculated at 146C and, as a way to eliminate the condensable fraction of the gas stream, is directed to a later radiator. This radiator can bring the temperature of the reformate to levels close to ambient temperature, proper condition to the refrigeration dryer. After the drying stage, now without most of the water previously presented as steam, the composition will be according to Table 4. The drying stage is very important because the integration of the reformer with the MPH2. This is due the fact that molecular sieves used for separation have high affinity to water, which

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adsorbs strongly on such materials and, in excess, can disrupt their crystalline nature, causing loss of performance of the purification step. Table 4. Reformate from ITSR, dry basis (T = 30 C , P = 1100 kPa). Species (mol/mol) H 2O 0,0032 H2 0,4321 N2 0,3390 CO 0,0144 CO2 0,1987 CH4 0,0124

4.2 H2 PURIFICATION MODULE (MPH2) Presented the logic of operation for MPH2, the sizing of this system took into account the fact that the columns propitiate to each other, purified H2 until the instant immediately prior to its blown-down.
H2 grade used in washing and equalizations ensures the columns, after regeneration and duly repressurisation, are able to start adsorption step. This grade is close linked to the mechanical integration of the columns, which for the developed PSA will provide a pressure profile over time schematically represented in Figure 6.
Pressure Profile 12 10 8 (bara) 6 4 2 0 1 11 21 31 41 51 61 71 (s) 81 91 101 111 121 131 141

Figure 6. Pressure profile in one adsorption column, through one complete cycle. According to the profile shown in Figure 6, its possible to determine the minimum operating pressure of one adsorber bed, pressure at which the amount of adsorbent should retain all the impurities removed from the load during the adsorption step. This column should contain the pressure holding capacity of gaseous impurities so as to provide proper H2 for purging of another column. The performance of MPH2, in terms of the Operational Time Unit (OTU - time period common to the purification steps) and the number of OTU in adsorption step, will provide a lean gas to overheater, as shown in Figure 7. For the reformate coming from the FPM (Table 4), OTU = 7s and number of OTU in adsorption = 6, the projected RI is 72.7%.

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Raffinate
0.6

0.5 0.4 (mol/mol)

0.3

0.2 0.1

H2 N2 CO2 CO CH4

0 40 45 50 55 60 IR PSA (%) 65 70 75 80

Figure 7. Relationship between RI and species distribution in lean gas from PSA.

5. DISCUSSION
With the design presented, the main inputs and outputs of the pilot plant can be summarized as shown in Table 5. Table 5. Main inputs and outputs of the H2 production pilot plant. Stream Inlet Outlet EtOH (L/h) 12,15 2 H2O (L/h) 14,44 10,38 3 Air (Nm /h) 18,92 3 3 H2 (Nm /h) 19,02 3 4 H2 (Nm /h) 13,82 1 Assumed boundary conditions: Tinj: 450C; Pop: 1200 kPa; TITSR: 300C. 2 Estimated amount of water removed from the gas stream after ITSR. 3 Partial flow of H2; 4 H2 flow output of MPH2.
1

Recycle 12,15 4,06 18,92 19,02 13,82

With the assumed boundary values of the process, the efficiencies related to the integrated unit of H2 production will be as shown in Table 6. Table 6. Efficiencies of the integrated unit head equipments. Efficiency (%) 77,5 ATR 72,5 ATR + ITSR CO Conv. ITSR 84,7 72,7 PSA 52,7 Overall Energy Efficiency It should be noted that the integration condition proposed with rated injection temperature of 450C, there is the availability of approximately 8 kW t leaving the overheater, energy that if harnessed in cogeneration, would imply an overall energy efficiency of 74.4 %. In line with previous estimations and preliminary experimental evidences, such performance is assured with approximately 6.7 kWhe for the balance-of-plant, which results in the value 0.48 3 kWh/m H2, a ratio which gives to the concerned thermochemical process an electricity consumption about 10 times less intensive than the production by water electrolysis. This aspect is crucial in direct competition of technologies, especially in niches applications which is located in areas where the electric grid is overloaded or close to this condition.

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6. CONCLUSIONS
This paper aimed to report the current development stage of the ethanol processor for H2 production pilot plant. The unit, besides the ethanol reforming, integrates H2 purification through PSA process, unit with nominal production rate of 1 kg/h H2 (4.5). Primary results were obtained through simulation routines specially developed for project and design of thermochemical systems of this nature, guiding the construction of the pilot plant. The results are consistent with international benchmark performance, of systems such as presented here. Views of the H2 production pilot plant are presented in Figure 8.

Figure 8. Views of the integrated unit of H2 production from autothermal reforming of ethanol. The integrated unit is early in its test schedule, which must validate the nominal values of design and add refinements to the theoretical work.

7. ACKNOWLEDGEMENTS
The authors would like to thank Fundao de Amparo a Pesquisa do Estado de So Paulo (FAPESP) for financial support as well Coordenao de Aperfeioamento de Pessoal de Ensino Superior (CAPES) and Conselho Nacional de Desenvolvimento Cientfico e Tecnolgico (CNPq). Thanks are also addressed to Hydrogen Laboratory (LH2 - Unicamp) for institutional support.

8. REFERENCES
[1] Grace Davison. (2008). SYLOBEAD: Adsorbents for Process Applications Brochure. Columbia, MD, USA: Grace Davison. [2] BASF. Performance communication of the catalyst SP-01 between Patrick Amrhein, PhD. and Antonio Marin. 2009.