Green Nylon
Dr. Xiucai Liu
January, 2012
Cathay Industrial Biotech Introduction
Nylon Industry Overview
Biobased (green) Nylon Monomers
Cathay Green Nylon Project
2
Cathay Industrial Biotech Overview
Largest biobutanol producer globally
2011 Sales: >7 million gallons
Leading bioprocess LCDA producer globally
Replacing Chemical Process
Leading international customer base
3
Cathay Project History
1997
2001
2003
2006
2007 – 2008
built first plant
Series A & B
Financing
Series C
Financing
2009
2010
2011
Corporate Milestones
Company
founded
Achieved
revenue of
>US$150 mn
Long Chain Diacid Milestones
began R&D
began
commercial
production
expansions
major DC12
supplier globally
developed
next generation
process
100,000 MT
plant built
cellulosic
biomass tech
breakthroughs
Biobutanol Milestones
board approves
biobutanol
project
30,000 MT
capacity built
Green Diamine Milestones
began R&D
technology
breakthroughs
acquired
commercial
lysine facility
I+G Milestones
technology
breakthroughs
pilot completed
4
Scale-Up Track Record at Cathay
Our integrated biotechnology platform has succeeded at commercial scale up—twice already
Lab
Pilot
Commercial
< 30 Liters
1-35,000 Liters
0.2-1.8 million Liters
1x
1,000x
100,000x
5
Cathay Long Chain Diacid Production Facility
6
Cathay Butanol Biorefinery
7
Cathay Management Team
Dr. Xiucai Liu
Founder, Chairman & CEO
led China national vitamin C bioprocess commercialization research project
20+ Years Industry Experience
Joachim Rudolf
CFO
∗
former CFO of HBM Bioventures
20+ Years Finance Experience
Professor Qixian Zhang
Co-Founder, SVP R&D
drafted biotechnology section of China’s national 5 yr plan for past 30 years
30+ Years Industry Experience
Paul Caswell
EVP Business Development
former VP of new technologies at ADM
30+ Years Industry Experience
Naiqiang Li
VP of Technology
10 Years Industry Experience
involved in every Cathay project since 2001
8
International Investor Backing
9
Cathay Industrial Biotech Introduction
Nylon Industry Overview
Biobased (green) Nylon Monomers
Cathay Green Nylon Project
10
World Fiber Consumption
1980-2010 total fibers CAGR:
2.8%
1980-2010 synthetic fibers CAGR: 4.9%
90
2010 synthetic fibers consumption:
80
million metric tons
nylon 6,6
70
synthetic
60
cellulosic
nylon 6
other
92%
natural
50
6%
2%
40
30
>3.7 million Ton nylon fibers market in 2010
20
10
0
1980
1990
2000
2010
ref:
-The Fiber Year LLC, Nov 2011, 9th China International Polyamides and Intermediates Forum, Shanghai, China
-Radici Group, Nov 2011, 9th China International Polyamides and Intermediates Forum, Shanghai, China
11
Nylon Price Projections
Estimated market price, US dollars/kg
Product
at $90/bbl crude oil
at $120/bbl crude oil
Nylon 6 filament
3.5
4.4
Nylon 6 polymer
2.9
3.5
Nylon 6,6 filament
3.7
5.1
Nylon 6,6 polymer
2.9
3.8
ref:
-Tecnon Orbichem, Nov 2011, 9th China International Polyamides and Intermediates Forum, Shanghai, China
12
Global Nylon Market
2010 Nylon 6 + Nylon 6,6 Estimated Market Size: ~$20 Billion USD
2010 Global demand, 6.5 million metric tons:
2.9
2.2
plastic
nylon 66
fiber
3.7
fiber
nylon 6
plastic
6.0
3.0
5.0
2.5
4.0
2.0
nylon 6 plastic
3.0
nylon 66 fiber
1.0
1.0
nylon 66
nylon 66 plastic
1.5
nylon 6 fiber
2.0
nylon 6
4.3
0.5
0.0
0.0
2010
2015
2010
2015
ref:
-Radici Group, Nov 2011, 9th China International Polyamides and Intermediates Forum, Shanghai, China
-Tecnon Orbichem, Nov 2011, 9th China International Polyamides and Intermediates Forum, Shanghai, China
13
Nylon Fiber End Uses
2010 Nylon fiber demand by end market
(million metric tons)
textile filament
carpet filament
staple fibre
industrial filament
1.2
1.5
0.2
0.7
ref:
-Radici Group, Nov 2011, 9th China International Polyamides and Intermediates Forum, Shanghai, China
-American Chemistry Council, December 2011. "Chemistry & Light Vehicles"
14
Forecasted Nylon Demand for Vehicles
lbs nylon per vehicle
total light vehicle nylon demand forecast
46
3.00
44
continue at current rate of increasing nylon
adoption in vehicles
Base case
2.50
millions metric tons
42
40
38
36
CAGR 6.5%
CAGR 4.4%
2.00
1.50
1.00
0.50
34
0.00
32
2001
2003
2006
2010
2011
2012
2013
2014
2015
2016
2017
2018
ref:
-American Chemistry Council, December 2011. "Chemistry & Light Vehicles”
-The Fiber Year LLC, Nov 2011, 9th China International Polyamides and Intermediates Forum, Shanghai, China
15
Nylon Production
nylon 6 and nylon 6,6 are the two most commonly used nylons
first commercial nylon was nylon 6,6 (PA 6,6)
synthesized by Wallace Carothers at Dupont in 1935
formed by reacting diamine (HMDA) with diacid (adipic acid)
PA 6,X nylons still produced today by reacting HMDA with diacids
nylon 6 (PA 6) subsequently developed by Paul Schlack at IG Farben
similar properties to PA 6,6, avoid Dupont patent
single bifunctional monomer (one acid and one amine end), self polymerizes
PA 6 produced from cyclic monomer caprolactam (CPL), PA 12 from laurolactam
16
Polyamide 6,6 Supply Chain
naptha
reformer/
separator
benzene
cyclohexane
adipic
acid
nylon
6,6
naptha
FCC/sepa
rator
butadiene
or
naptha/
natural
gas
olefin/crac
ker
propylene
adiponitrile
HMDA
acrylonitrile
controlled by Invista and Rhodia
ref: SZ Consulting, 9th China International Polyamide & Intermediates Forum in Shanghai, China November 2011
17
US Butadiene Price, Historical and Forecast
2005-2011 CAGR: 20%
3500
Dollars/Metric Ton
3000
2500
2000
1500
1000
500
0
2005
2006
2007
2008
2009
2010
2011
2012
2013
2014
2015
ref: Chemical Market Associates, Inc.
18
Cathay Industrial Biotech Introduction
Nylon Industry Overview
Biobased (green) Nylon Monomers
Cathay Green Nylon Project
19
Biobased Monomers/Polymers Under Development
Cathay’s bioprocess diacids are first example to take significant chemical market share
Product
Feedstock
Process
Company
1,4-butanediol (BDO)
bio
bio
Genomatica
1,3-propanediol (PDO)
bio
bio
Dupont, Tate&Lyle
polyethylene terephthalate (PET)
bio
chem
Toray
polyhydroxyalkanoates (PHA)
bio
bio
Metabolix
polylactic acid (PLA)
bio
bio
Natureworks
caprolactam (CPL)
bio
bio+chem
Draths
diamine (DN5)
bio
bio
Cathay
long chain diacid (DC11-18)
bio/chem
bio
Cathay
sebacic acid (DC10)
bio
chem
Casda Biomaterials
succinic acid (DC4)
bio
bio
BioAmber/Myriant
20
Nylon was inspired by natural polyamides (proteins)
proteins are natural polyamides
nylons are synthetic polyamides
Nylon 6,6
Fibroin (structural core of silk)
Nylon 6
21
Nylon Monomers From Renewable Sources
Oleic acid oxidation to azelaic acid
CH3(CH2) 7CH=CH(CH2) 7COOH ---[O3+catalyst]--> COOH(CH2) 7COOH
(DC9)
Castor oil conversion to nylon 11 and sebacic acid (DC10)
ref: Jean-Francois Devaux, Guillaume Le, Bernard Pees. (Arkema) “Application of eco-profile methodology to polyamide 11”
22
Nylon Monomers From Amino Acids: Lysine
Cathay lysine to pentamethylenediamine (DN5)
Wallace Carothers invented PA 5,10 before 6,6, preferred 5,10 for superior properties
DN5 chemical synthesis too expensive to commercialize
lysine to DN5 via decarboxylase studied academically, Cathay technology commercially viable
Lysine NH2(CH2)4CHNH2COOH
NH2(CH2)5NH2
(DN5)
Draths chemical catalysis of lysine to caprolactam (CPL)
Draths lysine to caprolactam through chemical catalysis
ref: John W. Frost. “Synthesis of Caprolactam from Lysine,” United States patent no. 7,977,450
23
Nylon from Amino Acids: Glutamatic Acid
HOOC(CH2) 2CHNH2COOH
HOOC(CH2)3COOH (DC5)
HOOC(CH2) 2CHNH2COOH
HOOC(CH2)3NH2 (PA5 monomer)
Gamma-polyglutamic acid (PGA)
image from http://www.stsicn.com
1:3500 water absorbance
China national research grant for Cathay to commercialize
24
Cathay Industrial Biotech Introduction
Nylon Industry Overview
Biobased (green) Nylon Monomers
Cathay Green Nylon Project
25
Cathay Green Nylon Project
bioprocess long chain diacids (LCDAs)
green diamine (pentamethylenediamine) technology
green nylon
Green Raw Material
H2N-(CH2)n-NH2
Green Diamine
Green Raw Material
HOOC-(CH2)m-COOH
Green Diacid
-[HN-(CH2)n-NH-CO-(CH2)m-CO]xGreen Nylon (Polyamide)
26
Cathay Green Nylon Project
bioprocess long chain diacids (LCDAs)
green diamine (pentamethylenediamine) technology
green nylon
Green Raw Material
H2N-(CH2)n-NH2
Green Diamine
Green Raw Material
HOOC-(CH2)m-COOH
Green Diacid
-[HN-(CH2)n-NH-CO-(CH2)m-CO]xGreen Nylon (Polyamide)
27
Diacid Bioprocess Alternative to Chemical Synthesis
Process Comparison
Competitive Landscape
Bio-Based Process
Paraffin
LCDAs
CH3-(CH2)n-CH3
Or
Or
Fatty
Acids
CH3-(CH2)n- COOH
(Renewable Source)
Green
LCDAs
Micro-organism
Standard Chemical Based Process
INVISTA
OH
Butadiene
Ti/AI
H2
CDDT
Air
CDD
COD
O
HNO3
CDDA
CDDK
LCDAs
Ube(1)
Evonik Industries AG
VCH
Multiple Chemical Steps
(1) Ube uses a similar chemical-based benzene process
28
Bioprocess Long Chain Diacids History
Prior efforts on long chain diacid bioprocess, without successful commercialization, by:
General Electric, Henkel, Purdue University collaboration funded by U.S. DOE in 1999
Dupont
Japan Energy
many companies using licensed Chinese Academy of Science technology
ref: Biosynthesis of Long-Chain Dicarboxylic Acid Monomers From Renewable Resouces, Final Technical Report. David P. Mobley, GE
Corporate Research and Development, April 1999, Prepared for US DOE Under Cooperative Agreement No. DE-FC36-95GO10099
29
In Collaboration with Customers,
Cathay developed All QC parameters
Even for “drop in” products, bioprocess impurities are a novel, significant challenge
dedicated simulation testing of downstream customer applications
process optimization focused on reducing costs to meet QC specifications
Many rounds of:
Process Breakthroughs
Industry customer feedback
novel product specifications developed to satisfy customer quality needs
custom analytical techniques developed for quality control
repeated rounds of customer feedback to refine QC specs and model.
Cost competitive, polymer grade, bioprocess-based LCDA
30
Long Chain Diacid Applications Developed by Cathay
Water absorption of long-chain diacids
6
10
Novel polymers
12
13
14
15
Peptide linkers for novel pharmaceuticals
Novel adhesives
PA 6,X
Anti-corrosion: PureMix
DC12
Car body coating:
Thinner and better
C-Shield
DC10
PureMix
DC12
31
Successful Customer Collaborations
-Cathay is only bioprocess dodecanedioic acid (DC12) supplier since 2004
-Cathay developed and supplies 100% of a new diacid used in transparent polyamide
-in 2007, Cathay supplied superior substitute for sebacic acid in hot melt adhesives
32
Replacing the Chemical Production Process
Cathay diacid sales volume
China diacid exports
100%
Cathay
90%
others
80%
70%
99.0%
60%
50%
40%
1.0%
30%
20%
10%
ref: China customs records
0%
2003
2005
2008
2011*
33
Cathay Green LCDA
34
Cathay Green Nylon Project
bioprocess long chain diacids (LCDAs)
green diamine (pentamethylenediamine) technology
green nylon
Green Raw Material
H2N-(CH2)n-NH2
Green Diamine
Green Raw Material
HOOC-(CH2)m-COOH
Green Diacid
-[HN-(CH2)n-NH-CO-(CH2)m-CO]xGreen Nylon (Polyamide)
35
Cathay Green Diamine Process
Sugar
fermentation
Lysine
NH2-CH2-CH2-CH2-CH2-CH-COOH
l
NH2
decarboxylation
DN5
NH2-CH2-CH2-CH2-CH2-CH2-NH2
36
Cathay Technology Improvement
Lysine to DN5
2008
Current
DN5 yield from Lysine
low
~100% of theoretical
conversion cost
~$1.50/lb DN5
< $0.05/lb DN5
37
Cathay’s Commercial Scale Lysine Facility
38
Cathay Green Nylon Project
bioprocess long chain diacids (LCDAs)
green diamine (pentamethylenediamine) technology
green nylon
Green Raw Material
H2N-(CH2)n-NH2
Green Diamine
Green Raw Material
HOOC-(CH2)m-COOH
Green Diacid
-[HN-(CH2)n-NH-CO-(CH2)m-CO]xGreen Nylon (Polyamide)
39
Nylons From PMDA (DN5)
Nylon 5,10
higher tensile strength than silk
more elastic than silk
superior chemical and moisture resistance compared to nylon 6,6
Nylon 5,6
melting point between nylon 6 and nylon 6,6
directly address significant portion of both 6 and 6,6 market applications
demand pull for green engineering plastic
Nylon 5,4
high melting point, potential substitute for aromatic based polymers
100% green combined with bioprocess succinic acid
Nylon 5,X
PA 5,12 using Cathay renewable DC12 would also be 100% green
PA 5, T substitution for PA 6, T
potential range of novel polymers from X=11-18, exclusively available from Cathay
40
Nylons: existing and novel
Commercially sold
Bio monomers from Cathay
nylon
diamine
diacid
unit length
nylon
diamine
diacid
unit length
PA 4,6 (Stanyl)
4
6
10
PA 5,4
5
4
9
PA 6,6
6
6
12
PA 5,6
5
6
11
12
PA 5,T
5
8
13
PA 6
PA 6, T
6
8
14
PA 5,10
5
10
15
PA 6,10
6
10
16
PA 5,11
5
11
16
PA 6,12
6
12
18
PA 5,12
5
12
17
PA 6,14
6
14
20
PA 5,13
5
13
18
PA 10,10
10
10
20
PA 6,12
6
12
18
PA 10,12
10
12
22
PA 6,14
6
14
20
22
PA 10,12
10
12
22
24
PA 12,12
12
12
24
PA 11
PA 12,12
PA 12
12
12
24
41
Cathay Green Nylon Milestones
2001
Long
Chain
Diacids
Diamine
Nylon 5,X
technology
development
2002
2003
2008
pilot study
commercialization
2010
2011
2012
replaced chemical process for
significant market share
technology development
2013
expand market size
pilot study
commercialization
pilot study
commercialization
42
Thank You!
43