achievements of the supergen dosh 2 project

Achievements of the SuperGen DoSH2 ProjectJohn TS IrvineBirmingham 18/10/11

http://www.uk-cpi.com/index.html

xxxxation Title To Go Here

Hydrogen Production


Current Hydrogen Production


Energy Devolution

Energy

Transport

Electricity

Heat

Chemicals

University of St Andrews. John Irvine Newcastle University. Ian S Metcalfe University of Manchester, JC Whitehead Cambridge University, Bartek Glowacki, University of Birmingham, David Book Strathclyde University, Shanwen Tao Andrew Cruden David Infield.

Imperial College,. Kang Li Marcello Contestabile.

University of Warwick, Martin Wills Cardiff University, Neil B. McKeown Oxford Chemistry, Edman Tsang Cardiff University, Malcolm Eames Leeds University, Valerie Dupont

12 Universities £5M 71 man-years6 PhD Students and 500 researcher months

WP1H2 from carbonaceous sourcesIan Metcalfe

Combined reaction and separation using:Membranes Periodic reactor operation

chemical looping membrane operation

redoxcycling

H2OH2

CO2

CO

ABO3

ABO3-d

periodic reduction/oxidation steps continuous process

Advantages of both processes:

• feed gases do not mix• high purity H2 possible• no down stream separation

required

CH4

H2O H2O O + H2 H2

Syngas O2-

gas feeds and products separated in time gas feeds and products separated in space

hollow fibre membrane

Perovskite oxygen carriers for hydrogen production from two processes

x-section

CH4 + H2O CO + 3H2CO + H2O CO2 + H2

water-gas-shift steam reforming of methane

Example results: Products as a function of time. Plotted together are the products from the water-splitting side and the methane oxidation side. Syngas and hydrogen are produced; overall we have steam reforming. Continuous operation for over 400 hours is the longest reported to date for this process.

0 100 200 300 4000.0

0.2

0.4

0.6

0.8

1.0

Mole

frac

tion

/ %

Time / hours

H2 water splitting stream H2 syngas stream CO syngas stream

membrane operation

0 20 40 60 80 100 120 140 160 1800

25

50

75

H2 CO CO2

Mola

r Pro

ducti

on /

mol

Cycle Number

chemical looping

CH4 + H2O CO + 3H2CO + H2O CO2 + H2

Example results: Products as a function of cycle number. Plotted are the products from the water-splitting phase. High purity hydrogen is produced. We have done over 170 cycles, the most reported to date.

background levels of CO and CO2

850oC 900oC

Researchers in Manchester have developed a novel and promising technology – plasma-catalysis, for highly-efficient conversion of methane (in the form of biogas or landfill gas) into hydrogen and other value-added chemicals (carbon nanomaterials, oxygenates, etc). This process combines the advantages of fast and low temperature reaction from nonthermal plasma and high selectivity from catalysis. The physical and chemical interactions between the plasma and catalyst can generate a synergistic effect, which provides a unique way to separate the activation steps from the selective reactions at low temperatures. Plasma can also reduce and activate supported metal catalysts, enhancing metal dispersion on the catalyst surface and catalyst stability, which opens a new route for catalyst treatment at low temperatures.

Low Temperature Plasma-Catalysis for Hydrogen Production from Methane

Warwick (Martin Wills)

WP 1.1 (Formation of hydrogen from alcohols) – work by TCJ.

Staff key: PDRA David Morris: DJMPhD Tarn Johnson: TCJ

FeOC H

PhOH

PhPh

OC

Ph

FeOC CO

SiMe3/PhO

SiMe3/Ph

OC

O

(iii) Synthesis of di-iron complexes for electrochemical hydrogen generation; subject of ongoing studies with Prof P. R. Unwin (Warwick).

(ii) Encapsulation of catalysts in a PIM membrane, and is testing in hydrogen transfer; open to return to in future (Cardiff/Warwick collaboration).

FeOC

FeTMS

OC

O

CO

COCO

CO

Ph

OCOC

OR

CO

OMe

OCOC

OR

CO

MeO

R=TBDMS, TMS, Ph

Ph Me

O 10 mol% iron catalyst/Me3NO

HCO2H/Et3N (FA/TEA) or Ph Me

OH

iPrOH R

H

Used in asymmetric reduction of ketones:Catalysts below:

Catalysts below: Used in oxidation of alcohols (below):

Catalystacetone +

OH O OH

(i) The application of iron-based cyclone catalysts to the synthesis of methanol, ethanol and isopropanol from large alcohols commonly found in biomass.

and for alcohol formylation (right):

10 mol% Fe catalyst10 mol% Me3NO.2H2O

Toluene, n eq. (CH2O)n60oC, 0.2 M, 3-6 h.

+R

OH

X

R

O

X

R

O

X

O

H

Warwick (Martin Wills)

WP 1.1 (Formation of hydrogen from alcohols) – work by DJM.Formation of hydrogen from alcohols using light-promoted process on inorganic support.

Hydrogen gas measurement by gas chromatography. Good progress has been made towards a synthetic catalysis system, as shown below:

Pt

VB

CBH2

N N

N

NN

NRu P

P

O

OHOH

OH

OHO

R1 R2

O

R1R2

OH

H

e-

e-

+ 2 H+

light (h)

Cat/Dye

TiO2 surface

N

TsN RuCl

Catalyst for hydrogen removal

N N

N

NN

NRu

HN

NHTsPh

Ph

2 PF6

Synthetic target molecule

Photo-sensitiser

The molecule shown below has been prepared and forms the basis of the targt supported system:

DJM has now left the HDel project to take up a position elsewhere; this work will be continued when a second PDRA is appointed at Warwick.

Staff key: PDRA David Morris: DJMPhD Tarn Johnson: TCJ

Amine-containing Polymers of Intrinsic Microporosity (PIMs)Mariolino Carta, Neil B. McKeown, Cardiff University (Chemistry).

PIMs provide microporous materials due to the rigid and contorted structure of the polymer.

We have found that Tröger’s base (TB) formation can be used as a polymerisation reaction starting from an aromatic diamine. This is a new way of making polymers (although the reaction was first reported in 1887).

N

NN

N

NH2

H2N

[CH2O]n

TFA

Two patent applications submitted (15/09/11)and now entering PCT phase.

The above TB-PIM combines:• High molecular mass (Mw >100,000 g mol-1 by GPC)

• Solubility in common solvents (e.g. chloroform, THF) and good film formation. • High apparent surface area (BET = 1000 m2 g-1)• Particularly selective for H2 in mixture of H2/N2 or H2/CH4

• (Note: data lie above Robeson upper bound in plots of permeability vs selectivity)

For example:


Hydrogen from Biomass and Waste

From Ethanol

SUPERGEN DOSH2:Delivery of Sustainable Hydrogen



Membranes and Separation

Ceramic

Metal



WP 2H2 from electronsJohn Irvine

Current-voltage (I-V) (2-electrode)47% H2O / 53% N2 | 900 °C | Conditioning: - 1.7 V, 2-5 min | Start potential: - 1.7 V | End potential: - 0.4 V | Scan rate: 10

mV s-1

• B-site doping acted to significantly lower the steam electrolysis onset potential

0

0.3

0.6

0.9

1.2

1.5

-0.205 -0.165 -0.125 -0.085 -0.045 -0.005

I (A cm-2)

- E (V

)

Composition Onset potential (V)

La0.4Sr0.4TiO3 - 1.21

La0.4Sr0.4Ni0.06Ti0.94O2.94 - 0.59

La0.4Sr0.4Fe0.06Ti0.94O2.97 - 1.04

La0.4Sr0.4TiO3

La0.4Sr0.4Ni0.06Ti0.94O2.94

La0.4Sr0.4Fe0.06Ti0.94O2.970.4

0.7

1

1.3

-0.015 -0.01 -0.005 0

I (A cm-2)

- E (V

)


1 wt% Pd-GDC co-impregnated LSCM cathode

-0.4 -0.3 -0.2 -0.1 0.0 0.1 0.20.0

0.5

1.0

1.5

2.0

Volta

ge /

V

Current density / A cm-2

CO2-CO 70-30

CO2-N2 70-30

CO2-N2 70-30 + 5% H2/Ar 0.849 V0.706 V

0.169 V

Polarization for CO2 electrolysis at 900oC

Polarization resistance (Ω cm2)

CO2/CO

ratio

Ni/YSZ

LSCM/ GDC

LSCM/ GDC-1%

Ni

GDC impregnated

LSCM

0.5Pd-GDC co-

impregnated LSCM

90/10 0.33 1.14 0.88 0.65 0.34

70/30 0.23 0.91 0.62 0.42 0.24

50/50 0.24 0.80 0.53 0.35 0.22



Electrolysis Liquifaction





AmmoniaProduction

Sociotechnical aspects


WP 3Sociotechnical economicsMalcolm Eames

ICEPT Techno-economic analysisOverview of research outputs to date

• Demand analysis of H2 as transport fuel– “Battery electric vehicles, hydrogen fuel cells and biofuels. Which will

be the winner?” Energy Environ. Sci., 2011, 4 (10), 3754 – 3772– “An analysis of the market for H2 fuel cell urban buses”, In preparation

• London case study – H2 from waste– “Assessing the role of H2 from waste in developing sustainable H2

infrastructures: a London case study” In preparation

• H2 for energy storage and UK-wide infrastructure– “The role of large scale storage in a GB low carbon energy future:

issues and policy challenges” Energy Policy 39 (2011) 4807–4815– “H2 from biomass: spatially explicit modelling can improve

infrastructure decision-making” Submitted to Int J Hydrogen Energy


Key Themes going forwardEnergy Storage to address intermittency

• Hydrogen can extend use of renewable or even nuclear electricity through storage. Excess power could be utilised for transport or chemicals moving renewable electricity to equally important sectors for CO2 reduction, i.e. transport and chemicals.

Hydrogen for transport• Hydrogen/fuel cell vehicles are a type of electric transport

closely linked with batteries. They offer range extension, long distance vehicles and greater payload. This can offer decentralised, largely self-contained energy systems with enhanced security.

Hydrogen in CO2 Capture• Converting hydrocarbons to H2 and CO2 or rather than

sequestering CO2, hydrogen can be utilised to capture CO2 to produce chemical feedstocks, fertilisers or liquid fuels.

achievements of the supergen dosh 2 project

Documents

high purity hydrogen

continuous operation

time gas feeds

landfill gas

h2oco2 h2watergas

nonthermal plasma

high selectivity

function of time