chemical looping membrane reformer concept for h2

Chemical looping membrane reformer

concept for H2 production and CO2

capture

J.A. Medrano, V. Spallina, M. van Sint Annaland, F. Gallucci

Chemical Process Intensification, Chemical Engineering and

Chemistry, Eindhoven University of Technology

XXII PIN Meeting

OUTLINE

Introduction

Novel reactor concept

Some results

Conclusions

PAGE 115-6-2014

H2 PRODUCTION…

PAGE 215-6-2014

… is continuously increasing for both chemical and energy industries, and it is

considered an ideal energy carrier for the foreseeable future.

Fossil fuels represent the main source for hydrogen production. More than

80% is produced by Steam Reforming (SR) of natural gas/methane in multi-

tubular fixed-bed reactors.

Main drawbacks:

Reaction system is endothermic and equilibrium limited Energy penalty

The large number of steps decreases the system efficiency

Moreover, anthropogenic CO2 emissions produce an important environmental

impact if adequate Carbon Capture and Storage (CCS) is not taken

CH4 + H2O ↔ CO + 3H2 ΔH°298K = +206 kJ/mol

800-1000 °C

20-35 atm

CO + H2O ↔ CO2 + H2 ΔH°298K = -41 kJ/mol

200-400 °C

Introduction

Reactor concept

Results

Conclusions

THE CO2 PROBLEM

PAGE 315-6-2014

CO2 is the main gas affecting the climate change. CO2 concentration in the

atmosphere has increased from about 280 ppm in pre-industrial period till 390

ppm in 2010.

REDUCTION IN EMISSIONS IS NECESSARY TO PREVENT CATASTROPHIC VARIATIONS IN THE EARTH

Introduction

Reactor concept

Results

Conclusions

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THE CO2 PROBLEM

PAGE 415-6-2014

CO2 is the main gas affecting the climate change. CO2 concentration in the

atmosphere has increased from about 280 ppm in pre-industrial period till 390

ppm in 2010.

The IPCC summarized in a report different mitigation strategies:

Chemical looping is one of the

most promising technology

among CCS strategies.

Introduction

Reactor concept

Results

Conclusions

H2 PRODUCTION WITH CO2

CAPTURE

PAGE 515-6-2014

Introduction

Reactor concept

Results

Conclusions

The goal is to develop an efficient process for hydrogen production with

integrated CO2 capture

Efficient: reduction in the number of steps in the steam reforming and the

achievement of auto-thermal operation.

CCS system: a pure CO2 stream provides an important contribution in the reduction

of CO2 emissions and thus climate change

Different systems have been proposed under this consideration


CAPTURE

PAGE 615-6-2014

Introduction

Reactor concept

Results

Conclusions

Other systems: Chemical looping concept

There is no reduction in the number of steps

An external purification system is needed (penalty)

• Methane reforming takes place in a

chemical looping reactor auto-thermal

operation

• For higher yields to hydrogen recovery, shift

reactors and PSA step are needed.

• The concept represents an improvement in

the global process efficiency.

M. Ortiz, et al. Int J Hydrogen Energy 36 (2011) 9663-9672

Auto-thermal process is achieved

A pure hydrogen stream is produced

Process efficiency is improvedCH4 + H2O ↔ CO + 3H2

ΔH°298K = +206 kJ/mol

CO + H2O ↔ CO2 + H2

ΔH°298K = -41 kJ/mol

Me + O2 ↔ MeO

ΔH°298K <<0

“The goal is to develop an efficient process for hydrogen production with integrated CO2 capture”

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CAPTURE

PAGE 715-6-2014

Introduction

Reactor concept

Results

Conclusions

Other systems: Steam Methane Reforming – Chemical Looping Combustion

There is no reduction in the number of steps

CO2 is produced at atmospheric conditions

• Steam reformer is placed inside a fuel

reactor of a CLC auto-thermal operation

• For higher yields to hydrogen recovery, shift

reactors and PSA step are needed.

• CO2 can be easily separated

M. Ryden, et al. Int J Hydrogen Energy 31 (2006) 1271-1283


A pure hydrogen stream is produced at high

pressures

Process efficiency is improved

CH4 + H2O ↔ CO + 3H2

ΔH°298K = +206 kJ/mol

CO + H2O ↔ CO2 + H2


Me + O2 ↔ MeO

ΔH°298K <<0













CAPTURE

PAGE 815-6-2014

Introduction

Reactor concept

Results

Conclusions

Other systems: Fluidized bed membrane reactors

Reduction in the number of steps

Pure stream of H2 is produced

CO2 can be easily separated by H2O condensation


Lower reaction temperatures

F. Gallucci, et al. Top Catal 51 (2008) 133-145

• Reforming and water gas-shift reactions are carried

out in the same unit.

• H2 extraction through the membranes displaces the

thermodynamic equilibrium towards products.

• Heat is supplied by hydrogen combustion inside the

U-shaped membrane Auto-thermal operation

Up to 30% of extra Pd membrane surface is needed

Part of the hydrogen produced is consumed in-situ
















6-2014

Introduction

Reactor concept

Results

Conclusions

MEMBRANE ASSISTED CHEMICAL

LOOPING REFORMING REACTOR

The novel reactor combines the advantages of the other systems and

solves their drawbacks

VIDI project ClingCO2 – project number 12365

Reduction in the number of steps


A pure hydrogen stream is produced

CO2 is easily separated by H2O vapor condensation

Lower reaction temperatures

• Reforming and water gas-shift reactions

are carried out in the same unit.

• Heat is supplied by a warm oxygen carrier

coming from the air reactor.

• H2 extraction through the membranes

displaces the thermodynamic equilibrium

towards products.Me + O2 ↔ MeO

ΔH°298K <<0CH4 + H2O ↔ CO + 3H2

ΔH°298K = +206 kJ/mol

CO + H2O ↔ CO2 + H2


THE SYSTEM PROVIDES A HIGH DEGREE

OF PROCESS INTENSIFICATION











6-2014

Introduction

Reactor concept

Results

Conclusions

THERMODYNAMICS

All reactor concepts previously depicted have been analyzed with Aspen

Plus and the calculations are carried out at chemical equilibrium

General scheme of the different cases studied:

CH4

H2O

HT - heat

Pre-reformed

syngas (500°C)

Air Technologies:

SMR - CLC

CLR + WGS + PSA

FBMR

MA-CLR

HT - heat

Depleted air

Pure H2 (P,T)

CO2-rich stream +

unconverted fuel

6-2014

Introduction

Reactor concept

Results

Conclusions

THERMODYNAMICS

MA-CLRAssumptions

• MeO in solid (wt%)= 20%

• Min ΔPH2 : 0.2 bar

• Pressure permeate side: 1 bar

• Pressure feed side: 20 bar

• S/C=1.5 & O/C=variable

• H2 selectivity membrane: infinite

• Max solid T = 1200°C

0%

20%

40%

60%

80%

100%

600 700 800 900 1000

Co

mp

osit

ion

[%

of

H2

eq

.]

Temperature (°C)

H2 as eq.H2O

H2 as eq.CH4

H2 as eq.CO

H2 reten.

H2 recov.

0%

10%

20%

30%

40%

50%

60%

70%

80%

550 650 750 850 950 1050

Hyd

rog

en

re

co

ve

ry [

% o

f H

2e

q.]

Temperature [°C]

SR-CLC+WGS+PSA

CLR+WGS+PSA

FBMR

MA-CLR 1.5

6-2014

Introduction

Reactor concept

Results

Conclusions

THERMODYNAMICS

SMR - CLCAssumptions

• WGS eq T = 250°C

• PSA eff: 90%




• Pressure : 20 bar

0%

10%

20%

30%

40%

50%

60%

70%

80%

550 650 750 850 950 1050

Hyd

rog

en

re

co

ve

ry [

% o

f H

2e

q.]

Temperature [°C]

SR-CLC+WGS+PSA

CLR+WGS+PSA

FBMR

MA-CLR 1.5

0%

20%

40%

60%

80%

100%

600 700 800 900 1000

Co

mp

osit

ion

[%

of

H2

eq

.]

Temperature [°C]

H2 as eq.H2O

H2 as eq.CH4

H2 as eq.CO

H2 losses

H2 recov.

6-2014

Introduction

Reactor concept

Results

Conclusions

THERMODYNAMICS

CLR + WGS +PSAAssumptions

• WGS eq T = 250°C

• PSA eff: 90%




• Pressure : 20 bar

0%

20%

40%

60%

80%

100%

600 700 800 900 1000

Co

mp

osit

ion

[%

of

H2

eq

.]

Temperature (ºC)

H2 as eq.H2O

H2 as eq.CH4

H2 as eq.CO

H2 losses

H2 recov.

0%

10%

20%

30%

40%

50%

60%

70%

80%

550 650 750 850 950 1050

Hyd

rog

en

re

co

ve

ry [

% o

f H

2e

q.]

Temperature [°C]

SR-CLC+WGS+PSA

CLR+WGS+PSA

FBMR

MA-CLR 1.5

6-2014

Introduction

Reactor concept

Results

Conclusions

THERMODYNAMICS

FBMRAssumptions


• Min ΔPH2: 0.2 bar

• Pressure permeate side: 1 bar

• Pressure feed side: 20 bar

• S/C = 3.0

• %O2 in the vitiated air: 5%

• H2 selectivity membrane: infinite

0%

20%

40%

60%

80%

100%

600 700 800 900 1000

Co

mp

osit

ion

[%

of

H2

eq

.]

Temperature (°C)

H2 burnt

H2 as eq.CH4

H2 as eq.CO

H2 reten.

H2 recov.

0%

10%

20%

30%

40%

50%

60%

70%

80%

550 650 750 850 950 1050

Hyd

rog

en

re

co

ve

ry [

% o

f H

2e

q.]

Temperature [°C]

SR-CLC+WGS+PSA

CLR+WGS+PSA

FBMR

MA-CLR 1.5

6-2014

Introduction

Reactor concept

Results

Conclusions

THERMODYNAMICS

Hydrogen recovery with the different reactor concepts

Conclusions

SMR-CLC has an optimum around

800°C and provides pure CO2

CLR+WGS+PSA concept is only

interesting at very high temperatures.

Processes with membrane reactors

would provide higher hydrogen

recoveries.

MA-CLR presents identical results

as FBMR by working with lower S/C

ratios and initial investment costs.

0%

10%

20%

30%

40%

50%

60%

70%

80%

550 650 750 850 950 1050

Hyd

rog

en

re

co

ve

ry [

% o

f H

2e

q.]

Temperature [°C]

SR-CLC+WGS+PSA

CLR+WGS+PSA

FBMR

MA-CLR 1.5

RESULTS. Thermodynamics

PAGE 1615-6-2014

Technology Advantages Disadvantages

CLR

The CLR downstream technologies are

developed and commercialized

Possibility of retrofitting the existing plant

H2 and CO2 are produced and separated at high

pressure

CLR reactors under pressurized conditions (Solid

circulation, HT/HP cyclones, etc…)

H2 losses in the PSA process

High T or very high S/C ratio are required for high

performance (CH4 conversion)

SMR-CLC

The downstream technologies are developed

Possibility of retrofitting the existing plant

H2 is produced and separated at high pressure

H2 losses in the PSA process

High S/C ratio (typical of tubular SMR) are required

for high performance

CO2 is produced at atmospheric pressure

Very high solid circulation is required to operate the

FR-SR at high temperature

FBMR

Possibility to operate at the high pressure

High methane conversion at 600-700°C

High purity H2 separation

Conversion and Separation in only one unit

Part of the permeated H2 is burnt – High

membrane area is required (≈30% extra)

Very high S/C ratio is required to guarantee high

H2 production

MA - CLR

High performance at intermediate temperature

Adiabatic reactors

High S/C is NOT required

High purity H2 separation

Conversion and Separation in only one unit

The reactors are operated under pressurized

conditions

Technology complexity and challenge for the

reactor design

Permeated side pressure is limited to the

membrane area and the reactor pressure

Introduction

Reactor concept

Results

Conclusions

6-2014

Introduction

Reactor concept

Results

Conclusions

GENERAL CONCLUSIONS

ABOUT THE CONCEPT

The novel MA-CLR could provide a solution of several disadvantages of the

conventional technology for SMR, with some technological challenge

Hydrogen recovery in concepts with integrated membrane reactors is higher than in

traditional processes.

Auto-thermal reaction with integrated hydrogen production and CO2 capture could

be achieved in only one unit.

Lower S/C values (reducing energy penalty) and low membrane surfaces (reducing

cost) are needed with the novel concept proposed compared with FBMR.

The system represents a high degree of process intensification.

6-2014



Preliminary study:

Thermodynamics

Introduction

Reactor concept

Results

Conclusions

6-2014



Introduction

Reactor concept

Results

Conclusions

0%

10%

20%

30%

40%

50%

60%

70%

80%

550 650 750 850 950 1050

Hyd

rog

en

re

co

ve

ry [

% o

f H

2e

q.]

Temperature [°C]

SR-CLC+WGS+PSA

CLR+WGS+PSA

FBMR

MA-CLR 1.5

It has been demonstrated the

potential of the MA-CLR concept

compared to other novel reactor

concepts

6-2014



Preliminary study:

ThermodynamicsOxygen carrier

evaluation

Introduction

Reactor concept

Results

Conclusions

6-2014



Introduction

Reactor concept

Results

Conclusions

TGA experiments Packed bed

- Oxygen carrier conversion -Fuel conversion

-Selectivity to products

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 200 400 600 800 1000 1200

Co

nv

ers

ion

Time (s)

xred (500C)

xred (600 C)

xred (700 C)

xred (800C)

500

510

520

530

540

550

560

570

580

590

600

610

620

0

10

20

30

40

50

60

70

80

90

100

0 500 1000 1500

Tem

pera

ture

(°C

)

Dry

gas c

om

po

sit

ion

(%

)

Time(s)

CO CO2

CH4 H2

T bed

NiO + H2 Ni + H2O

2Ni + O2 2NiO

20% H2

600°C

S/C = 3

6-2014



Hydrodynamic study in

the membrane reactor

Preliminary study:


evaluation

Introduction

Reactor concept

Results

Conclusions

6-2014



Introduction

Reactor concept

Results

Conclusions

0 0.1 0.2 0.3 0.4 0.50.01

0.015

0.02

0.025

0.03

0.035

0.04

Height above distributor plate (m)

Bu

bb

le d

iam

eter

(m

)

FBR

FBMR full bed

SMR-staggered

SMR-inline

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.40

0.5

1

1.5

2

2.5

3

Height above distributor plate (m)

Bu

bb

le r

ise

vel

oci

ty (

m/s

)

FBR

FBMR full bed

SMR-staggered

SMR-inline

Solids circulation pattern

6-2014



Phenomenological

model



Preliminary study:


evaluation

Introduction

Reactor concept

Results

Conclusions

6-2014



Introduction

Reactor concept

Results

Conclusions

Combination of mass and heat balances with hydrodynamics.

Kinetics from the oxygen carrier evaluation

Permeation from membranes evaluation

Hydrodynamics from experimental findings

Bubble-wake phase

Cloud-emulsion phase

6-2014



Phenomenological

model

Detailed model of the

reactor



Preliminary study:


evaluation

Introduction

Reactor concept

Results

Conclusions

6-2014



Introduction

Reactor concept

Results

Conclusions

6-2014



Phenomenological

model


reactor



Preliminary study:


evaluation

Techno-economical

analysis

Introduction

Reactor concept

Results

Conclusions

6-2014



Phenomenological

model


reactor



Lab scale

demonstration

Preliminary study:


evaluation

Techno-economical

analysis

Introduction

Reactor concept

Results

Conclusions

6-2014



Introduction

Reactor concept

Results

Conclusions

6-2014



Phenomenological

model


reactor



Lab scale

demonstration

Preliminary study:

Thermodynamics

Pilot plant

demonstration

Oxygen carrier

evaluation

Techno-economical

analysis

Introduction

Reactor concept

Results

Conclusions

6-2014



Introduction

Reactor concept

Results

Conclusions

6-2014



Phenomenological

model


reactor



Lab scale

demonstration

Preliminary study:

Thermodynamics

Pilot plant

demonstration

Oxygen carrier

evaluation

Techno-economical

analysis

Introduction

Reactor concept

Results

Conclusions

ACKNOWLEDGMENTS

PAGE 3415-6-2014

NWO/STW for the financial support through the VIDI project

ClingCO2 – project number 12365

-Dr. F. Gallucci,

-Prof. M. van Sint Annaland

-Dr. I. Roghair

-Dr. V. Spallina

-R. Voncken

XXII PIN Meeting

chemical looping membrane reformer concept for h2

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