Membranes for Industrial Applications

Claudia Staudt, GMM/MBASF SE Ludwigshafenclaudia.staudt@basf.com

Content

Introduction

Membrane materials

Membrane types for industrial applications

Approaches for nanoporous membrane preparation

Nanocomposites in MF/UF and RO

Membranes in emerging applications

Summary

2

Sustainability will become even more important in the future

SUPPLY DEMAND

1976 2010

Annual regenerative capacity of the planet

Human beings now demand more from the Earth than can be regenerated

Earth’s resources

Consumption of Earth’s resources

+

Source: Accenture. 3

BASF targets for water management

Abstraction of drinking waterfor production

by 2020 (baseline 2010)

Sustainable water management

at sites in water stress areas by 2020

+100%-50% Status 2011:-20.9%

Status 2011:+2.0%

4

BASF targets towards water emissions

Organic substancesby 2020

(baseline 2002)

-80% Status 2011:-73.5%

*assuming comparable product portfolio 5

6

Innovation focus moves from molecules to materials and solutions

Chemistry as key enabler for functionalized materials & solutions

Deep understanding of customer value chains required

New molecules

Improved applications

Functionalized materials & solutions

1960 1970 1980 1990 2000 2010 2020

Batteries, membranes ...

From chemicals to chemistry

1930s: invention of PVP by Prof. Reppe at BASF

1980s: PES/PVP

membranes for dialysis

2012: new PVP copolymer for

membranefunctionalization

BASF as membrane material supplier

Luvitec VA 6535 P®

N OO

CH3

O

n m

7

O

O S

O

Polysulfone, Polyethersulfone: membrane material

m

n

Polyvinylpyrrolidone: pore modifier, surface modification

Moving towards sustainable system solutions

Acquisition of Inge Watertechnologies: extension of the value chain

raw materialsPES, PVP, NMP

elementsfibre, module, rack

standard package

system integrator

application

improved UF membrane by combination of material know how with the understanding of customer needs

leverage synergies to develop improved additives, flocculants and polymers

unique Multibore®

structure of membrane:

superior fiber stability

know-how in polymer and membrane

modification, surface

structuring 8

Water purification using membranes

contaminated water

analgesicasbestos

radioactivematerial

bacteria

hormone

beta-blocker

sedimentpesticidePAK

inorganic material

oestrogenantibiotics disp

osal

stre

am d

irect

ion

poremembrane

highly purified water9

Membrane types for different industrial applications

Size of molecule/particle [µm]

Diff

eren

tial p

ress

ure

[bar

]

10 10010.10.010.0010.00010.1

1

10

100

1000Forward osmosisReverse osmosisGas permeation

NanofiltrationUltrafiltration

MicrofiltrationParticle filtration

Solution-Diffusion Membranes

PorousMembranes

10

Membrane materials for water treatment processes

Polysulfone, Polyethersulfone

Polyvinylidenfluoride

Polypropylene, Polyethylene

Cellulose acetate

Polyacrylnitril

Polyamide

Ceramics…

MBR5%

MF22%

RO55%

NF5%

UF13%

11

12

Properties of polyethersulfon (Ultrason® E)

good pore size control

intrinsic low oligomer content

high porosity possible

high temperature resistance (Tg: 225°C)

membranes with good chemical stability

membranes with lower fouling due to higher hydrophilicitycompared to other membrane materials

0

0.010.01

0.02

0.03

0.04

0.05

0 10 20 30 40 50 60 70pore size (nm)

dj/d

rp PESUPVDF

Nijmeier, K, Membrane Technology Group, University of Twente, Netherlands, 2009

Phase inversion

Casting knife

Spreading polymer solution

Prepare polymer solution

Casting on the glass plate

Coagulation bathGlass plate

Fabrication of nanoporous membranes via phase inversion process

Posttreatment

13

Flat sheet membrane (cross-section)

Pore size: 10-40 nm

Pore size: micrometer range

Contaminated water

14

500 nm

Fabrication of nanoporous structures via amphiphilic block copolymers

via block copolymers self organizing block copolymers of styrene/ 4-vinylpyridine

homogeneous pore size distribution

effective pore diameter 8 nm

Nature materials, Vol. 6, December 2007, p. 99315

Fabrication of nanoporous structures via block copolymers with etchable domains

via block copolymers triblock copolymers (styrene/divinylbenzene/lactic acid)

cross-linked polystyrene domains

echable polylactic acid domains

Science, Vol 336, 15. Juni 2012, p. 1423 16

Nano-composite UF membranes

Jian Huang , Kaisong Zhang, KunWang , Zongl iXie , Bradley Ladewig , Huanting Wang, Fabrication of polyethersulfone-mesoporous silica nanocomposite ultrafiltration membranes with antifouling properties, Journal of Membrane Science, in print

nanoporous silica is used as additives

interconnectivity of pores & water uptake is increased

fouling reduced

17

Thin film nanocomposite membranes for desalination processes

Journal of Membrane Science 294 (2007) 1–7www.nanoh2o.com

nanoparticle in active layer

improved flux

less energy consumption

18

Thin film nanocomposite membranes for desalination processes

Increased hydrophilicity Increased porosity Antifouling due to silver nanoparticles

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Commercial membrane applications

chlor alkaline process

solvent recovery systems

concentration of pigments, dispersions and suspensions

food and biotech products: isolation and concentration

catalyst recycling

gas separation

waste water processing

20

Challenges: varying mixtures(hydrocarbons, metal ions, tensides)

mobile systems necessary

GeoPure AdvancedHydro System, in the Barnett Shale in May 2012

Membranes for emerging markets

Produced water from “fracking” processes

21

mine drainage generates tons of sulfuric acid/day

pyrite + water + air → sulfuric acid + iron (ground water)

sulfuric acid + soil + rock → elevated metal release into waterways and groundwater

remediation can take up to 30 y

> 200 000 polluting, abandoned mine sites globally

Environmental Earth Sciences, Discussion Paper, September 2012

Membranes for emerging markets

Mine waste management

& mine rehabilitation

22

Membranes for emerging markets

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Summary and outlook

number of commercially applied membrane materials is limited

promising approaches with nanocomposite materials

in oil, fracking and mining processes complex mixtures occur

development of hybrid processes & mobile systems necessary

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