1 13 June 2017

Membranes for CCS

- converting life science into industrial technology -

May-Britt Hägg

Department of Chemical Engineering, NTNU

TCCS-9, June 12-14th, 2017

Award Winner’s Lecture

2 13 June 2017

I will briefly take you through:

1. The very basic about membranes / history

2. Some examples of membranes in industry

3. The long road from lab to pilot scale for the FSC-PVAm

membrane commercialization

- With some side steps

3 13 June 2017

MEMBRANES – the nature’s own answer to the life cyclus; breathing

Your lungs are efficient membranes!

The enzyme carbonic

anhydrase (CA) helps to

transport CO2 as HCO3-

through the lung

membrane

The microporous membrane

in a blood oxygenator will help

the patient to breath

4 13 June 2017

Your kidneys are efficient membranes!

MEMBRANES – the nature’s own answer to the life cyclus- purifying the blood

If your kidney can’t funtion, this UF-module will do the job!

Hollow membrane fibres; Membrane area 0.9m2

Artificial membrane for hemodialysis

5 13 June 2017

Membranes for gas separation is a ”young technology”

1960’s: First commercial trial (He recovery from natural gas)

1960’s Loeb & Souriraja succeeded in making asymmetric (polymeric) membranes with thin selective skin; CA for RO applications

1970 the technique developed by L&S was used for the first gas separation membranes

Mid 1970 several patents registered – modules built for small scale applications

1977: DuPont patent for spinning of hollow fibres for high pressure applications; recovery of H2 from gas mixtures

1979 – 1980: Many polymers are identified for membrane gas applications

*

1981: Monsanto can deliver hollow fibres as composites major step in the development (Monsanto membranes are today Air Products)

1980 Development of membranes for gas applications picks up speed

1990 The development of new materials explodes – sophisticated polymers, inorganic and mixed matrix materials, nanocomposites, m.contactors

2000 Towards piloting and commercialization of new membranes

MB has started the research on PVAm-FSC Membrane

6 13 June 2017

Where are we today – nearly 40 years later?

• The basic understanding about the membrane materials, transport mehcanisms, physical properties of the gases and their potential interactions with the materials, gives us the possibility of designing membranes for separation of spesific gas mixtures

• Membrane materials developed for gas separation today are tailormade of sophisticated materials. They may contain selective carriers and separate the components both as molecules, complexed compounds and ions.

• The theoretical understanding must be combined with good engineering and modelling – hence documentation may show that sometimes hybrid process solutions are a good solution; – combination of membranes and traditional unit operations

7 13 June 2017

Basics: How does a membrane work?

The membrane will separate on basis of:

Molecular size and structure of gas components

Physical properties of gases (ideal / non-ideal)

Membrane material properties

Different transport mechanisms (dense or microporous membrane; organic – inorganic; fixed/not-fixed carriers..)

Process conditions (temperature, pressure, concentrations) and process design

Feed gas

Retentate

Permeate

8 13 June 2017

1. The very basic about membranes / history

2. Some examples of membranes in industry

3. The long road from lab to pilot scale of the FSC-PVAm

membrane commercialization

- With some side steps

9 13 June 2017

Membranes in industry - numerous possibilities 1

OIL & GAS INDUSTRY:

• Production of inert N2 from air

• Natural gas sweetening (CO2 removal

• Natural gas dehydration (H2O removal)

• Recovery of H2 from crackers / refineries

• Recovery of VOC (from terminals or buoy

loading of tankers)

On topside

On sea bed

At refinery

Recovery of VOC

10 13 June 2017

Membranes in industry - numerous possibilities 2

REMOVAL of CO2 from various gas streams:

• Power generation (CO2 from N2 in flue

gas)

• Cement production (CO2 from CaCO3 +

combustion in flue gas)

• Steel industry (in mix with H2 and CO)

• Waste incineration (harmful components?)

• Biogas upgrading to high quality fuel

(CO2-CH4 separation)

• Note: The concentrations and components

present are different depending on source,

hence the system must be tailored!

Coal fired

power plant

Cement plant

Upgraded biogas ready for

injection into the gas grid

11 13 June 2017

1. The very basic about membranes / history

2. Some examples of membranes in industry

3. The long road from lab to pilot scale of the FSC-PVAm

membrane commercialization

- With some side steps

12 13 June 2017

The FSC-membrane / a composite membrane; PVAm (polyvinylamine) on PSf (polysulfone)

• Facilitated CO2-transport is the

dominating mechanism

Flux equation

2 2 2 3CO H O H CO

2 3 2 3 3H CO NH H CO NH

3 3 2 3 2H CO NH H CO NH

2 3 2 2H CO H O CO

,

,0 , ,0 ,

A cAA A A l AC AC l

DDJ c c c c

l l

Right hand side:

1st term: solution-diffusion,

2nd term: facilitated transport

• For best performance:

• Presence of water is needed

• Driving force by using vacuum on

permeate side

• High feed flow rate

B BB

(N2, O2)

Feed PermeateSelective layer

l

Support

CO2

NH2

CO2

H2O HCO3-

H2O

CO2

NH3+

NH2

PVAm

CO2

13 13 June 2017

The long road - FSC-Membrane / a brief review

• From lab to pilot 2000 – 2016:

Commercial type HF modules – Air Products

1st step (2008):

Lab, d=5-7 cm

2nd step (2011):

bench-pilot,

Flat sheets, 0.5 m2

3rd step (2012 -

2014): Small pilot,

Flat sheets –> 2m2

Power plant, Sines +

Cement factory 1,

Brevik

4th step ( 2014):

preparing for

hollow fiber

module in lab

5th step (2012-2016):

joining forces with

Air Products in two

projects:

2013: Rig at Tiller

2015: Rig at

NORCEM 2

AP Hollow fibers,

4.2 – 10 m2

14 13 June 2017

The FSC-PVAm membrane in pilot tests:

1. EDP, Sines, Portugal, the FSC-membrane; flat sheets tested

2. NORCEM Cement plant at Brevik, Norway; the same membrane module as

above; tested for flue gas with 20% CO2

3. Tiller test site, Trondheim – Norway 2016

Scaling up to ~10 m2 – coating the

FSC-membrane in-situ on PSf hollow fibers

Flat sheets, ~2m2, -

durability demonstrated

towards SOx and NOx

In flue gas: ~13% CO2

Tested in EU-Nanoglowa

This cement-plant was chosen as

the official CO2 capture test site for

the cement industry in Europe

(ECRA)

2012

2014

15 13 June 2017

The importance of process simulation

16 13 June 2017

Challenges when scaling up the hollow fiber modules and design pilot going from lab to real gas exposure

Challenges in module design:

HF membranes must be coated in-situ method developed

Flue gas is delivered at atmospheric pressure must ensure an efficient flow pattern so the whole membrane area is used

Difficult to document separation performance on larger modules in lab set-up

Design of the module with feed intake/outlet must ensure minimum pressure drop

Based on pilot experience, valuable input for the large scale modules - ongoing

Challenges in pilot system design

• Flue gas composition and impurities differ much from various industries (power plants, cement plant,….)

• Process should be temperature controlled to avoid too much condensed water in system

• System must be prepared for shut-downs and start-ups of the main plant

• Simple, rough control/ instrumentation

Compliments of Air Products

17 13 June 2017

Time to let «our baby» go – milestone December 2016

– the FSC technology is licensed to Air Products

• Air Products PRISM® Membrane Divison, St. Louis, USA, prepare the modules

• Air Products AS in Kristiansand Norway, will build and deliver the CO2-systems

– important for the commercialization and adaption to spesific applications

• Both divisions have been important partners for our membrane development

• AP is the pioneering company for HF PRISM® membranes worldwide - the FSC-

PVAm membrane is based on these PSf membrane systems

• Currently we (NTNU) are collaborating with AP on the Technology Transfer in

order to prepare the commercial, large scale modules

18 13 June 2017

A sincere wish: I hope our FSC-membrane technology

will contribute to boost - CCS

Further:

• CCS is needed not only in energy production

but also in industrial processes

Realizing:

Mother Earth is

swetting!

The climate change is

causing:

Warmer, wetter and

More dramatic weather

– floods, draughts

Glaciers are smelting –

and biodiversity is

reduced

Source: IEA 2012

19 13 June 2017

Thank you for the recognition of my membrane research –

Thank you for the award Above all:

Thank you to all collegues and industrial partners over the years; and to NRC who have

made this research possible through basic research, knowledge building and innovation

projects, demo piloting

Thank you to TCCS9

20 13 June 2017

Thank you all for the attention, and remember:

• Membranes are part of nature from which we learn

• Membranes are part of our bodies – our life

• Membranes will play an important role

in industry and their strive for clean and

green process solutions in future

You need patience and perserverance if you truly believe in

your research! The road from lab to commercialization

may easily take 20 years!