líneas de investigación relacionadas con la tecnología de producción de … de lucas...

1

Departamento de Ingeniería Química

Facultad de Ciencias Químicas

Universidad de Castilla la Mancha

Antonio de Lucas Consuegra, Fernando Dorado, Paula Sánchez,

Amaya Romero, José Luís Valverde Palomino

Líneas de investigación relacionadas con la

tecnología de producción de H2 del Departamento

de Ingeniería Química de la UCLM

2

Índice

Procesos catalíticos convencionales de producción de H2.

-Reacción de desplazamiento de gas de agua

-Trireformado de CH4

Sistemas integrados catálisis-electroquímica (efecto NEMCA)

-Soportes electro-activos catiónicos (Na- Al2O3)

-Soportes electro-activos aniónicos (YSZ)

-Co-producción simultánea de H2 y C2s (electrocatálisis)

3

Uses of Syngas

H2/CO ratio to be fitted by WGS process

kJ/mol 41,1- H 0

222 HCOOHCO

Exothermic reversible reaction. Catalysts are required

Reacción de desplazamiento de gas de agua

4

Aims of the projects funded by Elcogas and Spanish institutions

• Construction of a plant for the (WGS) reaction and separation of H2

of high purity through poor syngas coming from gasification (2 vol%)

•Testing of commercial WGS catalysts

• Development of new techniques for the separation of H2 (WGS-MR)

•Other uses of syngas (Fischer-Tropsch project for diesel production)


5

• 19 bar • 350-500 ºC• H2O/CO: 2.4-4.7

Commercial catalyst CoMo

H2S, COS

5 N l/min


6

Pressure: 19 bar

Molar ratio H2O/CO: 2.4

STUDY OF EQUILIBRIUM AND PROCESS DESIGN (HYSYS)

xCO> 0.90


7

7

A.R. de la Osa y col., International Journal of Hydrogen

Energy 36 (2011) 44-51


Catalizador fresco

Catalizador

tratado con

corriente de S

H2O/CO: 2.4H2O/CO: 3.4

H2O/CO: 4.7

Commercial catalyst CoMo

8


La activación se produce al tratar el

catalizador por encima de 60 ppm de S El COS y el H2S consiguen la misma

activación

9

Conversión de gas natural y CO2 en productos

de valor. (Claridge y col., 1998).

Proceso más utilizado a nivel industrial

Reformado con vapor

CH4 + H2O CO + 3H2 Hº298 = 206,3 kJ/mol (1.1.)

Reformado seco

Oxidación parcial de metano

CO2 + CH4 2CO + 2H2 Hº298 = 247,3 kJ/mol (1.3.)

CH4 + ½ O2 CO + 2H2 Hº298 = -35,6 kJ/mol (1.4.)

Proceso exotérmico

CO + H2O CO2 + H2 Hº298 = -41,1 kJ/mol (1.2.)

Reacción de trireformado de metano

10

Ventajas

Tri-reformado

Combina procesos exo- y endotérmicos

Formación de coque

Obtención de relación H2/CO deseada

Proceso que combina Reformado seco, Oxidación parcial y Reformado con vapor

desarrollado por el grupo del Pofesor Song (Song y col, 2004).

CH4O2

CO2

H2

O

C

O

H2

3CH4 + CO2 + H2O + 1/2O2 7H2 + 4CO


Los gases procedentes de los gases de combustión de plantas de energía basada en

combustibles fósiles o de la gasificación de residuos sólidos pueden ser utilizados como

agentes reactivos para el tri-reformado de gas natural para la producción de gas de síntesis

11


30

40

50

60

70

80

90

100

0 50 100 150 200 250

Tiempo (min)

Co

nve

rsió

n (

%)

Ni/CeO2

Ni/Al2O3

Ni/SiC

Ni/YSZ

Ni/YSZ-O2

-40

-20

0

20

40

60

80

100

400 500 600 700 800

Temperatura (ºC)

Co

nv

ers

ión

(%

)

Condiciones

CH4-6 %

H2O-3 %

CO2-3 %

O2-0.6 %

Balance N2

100 ml/min

Influencia del soporte catalítico

12


0

10

20

30

40

50

60

70

80

90

100

0 50 100 150 200 250

Tiempo (min)

Co

nvers

ión

(%

)

CH4

CO2

0

0,5

1

1,5

2

2,5

3

0 50 100 150 200 250

Tiempo (min)

Rela

ció

n H

2/C

O

0

10

20

30

40

50

60

70

80

90

100

0 50 100 150 200 250

Tiempo (min)

Co

nvers

ión

(%

)

CH4

CO2

0

0,5

1

1,5

2

2,5

3

0 50 100 150 200 250

Tiempo (min)

Rela

ció

n H

2/C

O

CeO2-Ac

CeO2-Nit

Influencia del precursor metálico

13

Electrochemical Promotion of

Catalysis (EPOC)

Solid electrolyte

Reactives Products Catalyst film

Working electrode

Stoukides and Vayenas, J. Catal. 70 (1981) 137

Counter electrode

“In situ” electrochemical

control of the catalytic activity


14

VWR

Electrochemical Promotion of

Catalysis (EPOC)

Solid electrolyte

Reactives Products

rCatalyst film

Working electrodeACTIVATION

“In situ” electrochemical

control of the catalytic activity

Counter electrode

Electrocatalysis

re=I/(nF) Faradaic Process

I

I=0 I=0

I≠0

t t

r0 r0

r0+ re

rNon Faradaic Electrochemical Modification

of Catalytic Activity (NEMCA effect)r

r>>re Non Faradaic Processr

backspillover

Stoukides and Vayenas, J. Catal. 70 (1981) 137


15

METAL

O2- O2- O2-

O -

O2-

O -

O -

O -

O -

O -

O -

METAL

Na+ Na+ Na+

Na *

Na+

Na +

Na +

Na +

Na +

Na +

Na +

D A

D

D

D

A

A D

A

A

A

D

Source of electronegative promoter (ZrO2-Y2O3)

Source of electropositive promoter (Na- -Al2O3)

A

D

Na +

O -

NO

CO

H

C2H4

C3H6

+

-

Origin of the phenomenon of electrochemical promotion

An electronegative promoter (O2-) enhances the

chemisorption of an electroposite adsorbate

The origin of the NEMCA effect

is the modification of the

binding strength of chemisorbed

reactants

An electropositive promoter (Na+) enhances the

chemisorption of an electronegative adsorbate

A: Electron acceptor, electronegative adsorbate

D: Electron donnor, electropositive adsorbate

A + D PRODUCTS

(r products )=k. A. D

C.G.Vayenas, et al., Nature, 343 (1990) 625


16

FIC

FIC

FIC

FIC

CH4

N2

H2

02 (air)

WATER SATURATORS

VOLTALAB PGP-201

VoltaMaster 4

MSR128Software

HEAT EXCHANGER

TEMPERATURECONTROLER

System Control Micro GC

Brooks Smart ControlSoftware

COOLINGSYSTEM

GC

REACTOR

Outlet

Counter

electrode

Catalyst-working

electrode

Electric connections

Inlet

Reference

electrode

Thermocouple

Single chamber configuration (WP2)


17

1) Pt paste (P)

2) Pt paste + 3 % Pt/YSZ (PPY)

Na- Al2O3 pellet (sodium conductor)

Au paste + calcination 600 ºC, 1 h

New developed electrochemical catalyst

Calcination 600 ºC

+ Reduction step

0 1 2 3 4 5 6

0

1

2

3

4

5

(a)

P

PPY

(r

H2

/ m

ol

s-1 g

met

-1)

x 1

05

Time on stream / h

0 1 2 3 4 5 6

75

80

85

90

95

100

(b)

CO

2 s

elec

tiv

ity

/ %

Time on stream / h

0

10

20

30

40

50

PPY sample

CH

4 c

on

ver

sio

n /

%

CH4/H2O: 1 %/4 %,

6 L.h-1

T= 500 ºC

Catalytic results and open circuit conditions

The addition of a catalyst powder to the

electrode improved its catalytic

performance

–The presence of Pt nanoparticles

increased its resistance to C deposition

–Morphological modification of the

electrode

Sistemas integrados catálisis-electroquímica (efecto NEMCA).

Soportes electro-activos catiónicos

18

Characterization of the Pt based electrochemical catalyst

(a)

(b)

3D profiler image and SEM analysis of the Pt electrodes

Pt paste (P) Pt paste + 3 % Pt/YSZ (PPY)

(a)

1 m

(b)

1 m

XRD analysis

PPY 75 nm

P 500 nm

Sample Average Pt particle size

Better catalytic performance



19

Catalytic results under closed circuit conditions

0 1 2 3 4 5 6 7 8

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

rH

2

(r H

2 / m

ol

s-1 g

met

-1)

x 1

05

Time on stream / h

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

Vce

ll /

V

Vcell

SRM conditions 500 ºC

0 1 2 3 4 5 6 7 8

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

rH

2

(r H

2 / m

ol

s-1 g

met

-1)

x 1

05

Time on stream / h

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

Vce

ll /

V

Vcell


Conditions: CH4/H2O: 1 %/4 %, 6 L.h-1, T= 500 ºC



PPY

20


0 1 2 3 4 5 6 7 8

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

rH

2

(r H

2 / m

ol

s-1 g

met

-1)

x 1

05

Time on stream / h

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

Vce

ll /

V

Vcell


0 1 2 3 4 5 6 7 8

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

rH

2

(r H

2 / m

ol

s-1 g

met

-1)

x 1

05

Time on stream / h

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

Vce

ll /

V

Vcell


Conditions: CH4/H2O: 1 %/4 %, 6 L.h-1, T= 500 ºC

Pt

CH4

VWRAdsorption of electron donor (CH4)

Origin of electrochemical promotion phenomenon

C.G.Vayenas et al. Catal. Today 211 (1992) 303.

CH4

CH4

Na+

Na+

Na+C

H2

CH2

C

H2

H2O

H2O

H2O

CO2

CO2

V +V -

H2

H2

H2

CO2

EPOC allows to partially regenerate the catalyst from carbon deposition

VWRAdsorption of electron acceptor (H2O)



PPY

21


Influence of the reaction atmosphere

0 2 4 6 8

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

MPO

ATR

(r H

2 / m

ol

s-1 g

met

-1)

x 1

05

Time on stream / h

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

Vce

ll /

V

Vcell

500 ºC

0 2 4 6 8

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

MPO

ATR

(r H

2 / m

ol

s-1 g

met

-1)

x 1

05

Time on stream / h

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

Vce

ll /

V

Vcell

500 ºC

Conditions

-Methane Partial Oxidation (MPO): CH4/O2: 1 %/0.2 %

-Autothermal Reforming (ATR): CH4/H2O/O2: 1 %/4 %/0.2 %

T= 500 ºC

The increase in the chemisorption of O2 under negative

polarization allows to completelly regenerate the

catalyst from Carbon deposition

0 10 20 30 40 50 60 70 80

0,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

1,8

2,0

2,2

2,4

2,6

2 V

2 V_-1 V

(rC

O2 /

mol

s-1 g

met

-1)

x 1

07

Time / min

240

270

300

330

360

390

420

450

480

510

540

570

600

630

Tem

per

ature

/ º

C

Temperature

TPO analysis



PPY

22


Reproducibility of results

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

H2

2 V2 V2 V -1 V-1 V-1 V-1 V

(r H

2 / m

ol

s-1 g

met

-1)

x 1

05

0 2 4 6 8 10 12 14 16 18 20 22

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

CO

CO2

(r C

O, C

O2 /

mol

s-1 g

met

-1)

x 1

06

Time on stream / h

-Electrochemical promotion allows to completellyregenerate in an unlimited way the catalyticperformance of the system for the production of H2

-Almost no CO is formed during the experiment(WGS activity)

Conditions

-Autothermal Reforming (ATR): CH4/H2O/O2: 1 %/4 %/0.2 %

T= 500 ºC

Application for H2 production free

of CO for fuel cells



A.de Lucas-Consuegra y col., J. Catal. 274 (2010) 251–258

PPY

23

Pt paste + 3 % Pt/YSZ

YSZ (O2- conductor)

Au paste + calcination 600 ºC, 1 h


-Calcination 600 ºC

-Reduction step at 400ºC

Characterization of the active catalyst-electrode (SEM-EDX)

The dispersed Pt catalyst

powder is well mixed with

the Pt agglomerates

Working

Counter


Soportes electro-activos aniónicos

24

Catalytic results

0,0E+00

5,0E-07

1,0E-06

1,5E-06

2,0E-06

2,5E-06

3,0E-06

3,5E-06

4,0E-06

4,5E-06

0 50 100 150 200

Time/ min

rH2

, rC

O2

, rC

H4

/ m

ol s-

1 g

met

al-1

-60

-40

-20

0

20

40

60

I/ m

A

rH2

rCO2

rCH4

I

Conditions:

600 ºC, 1%CH4, 1.5%H20, 0,2 % O2, flow 100 ml/min

Pt

Au

O2-

Steam electrolysis

Electrocatalytic partial

oxidation of methane

Pt

Au

O2-

No electrocatalytic partial


Steam electrolysis

>10

Positive polarization

Negative polarization



25

Catalytic results

Conditions:

600 ºC, 1%CH4, 1.5%H20, 0,2 % O2, flow 100 ml/min

Pt

Au

O2-

Steam electrolysis

Electrocatalytic partial


Pt

Au

O2-



Steam electrolysis of water

Positive polarization


2,0E-07

2,2E-06

4,2E-06

6,2E-06

8,2E-06

1,0E-05

1,2E-05

1,4E-05

-220 -170 -120 -70 -20 30 80 130 180

I / mA

r H

2/

mo

l s-

1 g

met-

1

0,0E+00

5,0E-07

1,0E-06

1,5E-06

2,0E-06

2,5E-06

3,0E-06

3,5E-06

4,0E-06

4,5E-06

rCH

4/

mo

l s-

1 g

met-

1

rH2

rCH4

Steam electrolysis on Pt Steam electrolysis on Au

Electrocatalytic partial oxidation on Pt

NEMCA effect?



26

Catalytic results

0,0E+00

2,0E-06

4,0E-06

6,0E-06

8,0E-06

1,0E-05

1,2E-05

1,4E-05

0 50 100 150 200 250 300time/ min

rH2/ m

ol s-

1 g

met

-1

-160

-140

-120

-100

-80

-60

-40

-20

0

20

I/ m

A

CH4+O2

H2O + O2

CH4+H2O+O2

I

Conditions: 600 ºC, 1%CH4, 1.5%H20, 0,2 % O2, flow 100 ml/min

CH4, O2: No electrocatalytic partial oxidation of methane on Au

H2O,O2: Steam electrolysis, only at very negative potencials

CH4,O2,H2O: Steam electrolysis and Electrochemical Promotion of methane reforming on Pt

Pt

Au

O2-



Steam electrolysis


Production of H2 by

NEMCA in SRM

O2 H2O

Yentekakis, et al.,

Ionics 1995

VWR



27


Co-producción simultánea de H2 y C2s (electrocatálisis)

Proyecto Europeo Acenet. Simultaneous Production of Hydrogen and C2

Hydrocarbons in Solid Oxide Membrane Reactors.

ACENET ERA-NET VI Programa Marco de la Unión Europea

YSZ (O2- conductor)

Ag paste + calcination 800 ºC, 1 h


Impregnation Ni(NO3)2.6H2O, 0,1M solution in water

Calcination 800 ºC, 1 h, 5 ºC/min

Reduction: 600 ºC, 1h

Ni film

Characterization of the Ni catalyst film

-Continuous and porous Ni film.

-Good electrical conductivity after reduction:(resistance <15 Ω)

28

Catalytic results

0,0E+00

2,0E-08

4,0E-08

6,0E-08

8,0E-08

1,0E-07

1,2E-07

1,4E-07

1,6E-07

1,8E-07

0 20 40 60 80Time/ min

r H2/ m

ol s-1

-160

-140

-120

-100

-80

-60

-40

-20

0

20

Cu

rren

t (m

A) c

0,0E+00

2,0E-10

4,0E-10

6,0E-10

8,0E-10

1,0E-09

1,2E-09

0 20 40 60 80Time/ min

rc2/m

ol s-1

-160

-140

-120

-100

-80

-60

-40

-20

0

20

Cu

rren

t (m

A)

c

C2H4

C2H6

Current

Conditions: 850ºC, 1%CH4, 1.5%H20, 100 ml/min

Ni

Ag

O2-

Oxidative coupling of methane

Steam electrolysis


It is possible to simultaneouslly

produce H2 and C2 hydrocarbons in

a single chamber solid electrolyte cell

CH4+1/2O2H2O+C2H6

C2 yields up to 10 %

C2 selectivity up to 90 %

2CH4+O2 2H2O+C2H4


Co-producción simultánea de H2 y C2s (electrocatálisis)

29

Departamento de Ingeniería Química

Facultad de Ciencias Químicas

Universidad de Castilla la Mancha

Antonio de Lucas Consuegra, Fernando Dorado, Paula Sánchez,

Amaya Romero, José Luís Valverde Palomino

Líneas de investigación relacionadas con la

tecnología de producción de H2 del Departamento

de Ingeniería Química de la UCLM

líneas de investigación relacionadas con la tecnología de producción de … de lucas...

Documents