western coatings show – october 2015 new reds – pigment innovation
TRANSCRIPT
Western Coatings Show – October 2015
New Reds – Pigment Innovation
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Topics
Production processes for iron oxide red pigments1
4 Sustainable New Red pigments for the coatings market
2 Today´s Penniman Red Process
3 Tomorrow´s Penniman New Red Process
3
Synthetic Iron Oxides – a global market by color, region & application
By color [kt in %, 2013] By application [kt in %, 2013]
Global market for synthetic iron oxide pigments [~887kt in 2013]
Red
43%
Blen
ds 5%
Black
23%
Yellow
29%
By region [kt in %, 2013]
Americas
24%
EMEA
33%APAC
43%
Coatings
26%
Plastics 5%
Construction
48%Paper 3%
Other
18%
Source: IPG GPM market analysis
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What is sustainability?According to the EPA*
What is sustainability?Sustainability is based on a simple principle: Everything that we need for our
survival and well-being depends, either directly or indirectly, on our natural
environment. Sustainability creates and maintains the conditions under which
humans and nature can exist in productive harmony, that permit fulfilling the
social, economic and other requirements of present and future generations.
Sustainability is important to making sure that we have and will continue to
have, the water, materials, and resources to protect human health and our
environment.
*Obtained from the EPA United States Environmental Protection Agency website.
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Sustainability: Setting up new sustainability standards in iron oxide and chromium oxide business
Sustainability LANXESS is driver for
continuous HSEQ
improvements within the iron
oxide industry globally
Global sustainability approach
leads to more environmentally
friendly processes and products
LANXESS’ products are highly
efficient, sustainable and
without any harm to our health
or to nature (SCS certificate for
recycled content)
Focus on sustainability in all
production steps brings a
competitive advantage
CO2 neutral production of energy by using biomass
(Co-Generation plant – Steam & Electricity)
Reduction of CO2 emissions by 44kt annually
Porto Feliz,
Brazil
State-of-the-art waste water treatment plant Reduced emissions by improved energy utilization
and water management Black plant recycling by-product of yellow production
Jinshan,
China
Innovative waste water recycling
Processed water on the recovery unit does not
require further cleaning
Krefeld-
Uerdingen,
Germany
Penniman process was optimized
using waste water treatment and off-gas scrubbing The plant will have high energy efficiency, that
meets and exceeds the latest environmental standards
Future plant
Ningbo,
China
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“Laux Red” Process
Laux-Reaction
Milling
ClassificationFiltrationWashing
steam
Fe
wastewater
NitrobenzeneAdditives
Calcination
Raw Aniline
Aniline
Damping Destillation
H2
to power plant
exhaust gasessulfacite
plant
“Copperas Red” Process
FeSO4 x 7H2O
Purification Crystallization
Dehydration FeSO4 x H2O
Calcination
WashingFiltration
SO2 SO3
Metalsulfates
Contact sulfuric
acid plant
Red FEO Red FEO
Drying Milling
3. Penniman-Reaction
Red FEO
Filtration,Washing
1. Iron nitrate
Air
Steam
HNO3
NOx
2. Seed
Waste-water
HNO3Fe
Drying (and Milling)
“Penniman Red” Process
All industrial Red FEO production processes require special treatment for sustainable operation
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Topics
Production processes for iron oxide red pigments1
4 Sustainable New Red pigments for the coatings market
2 Today´s Penniman Red Process
3 Tomorrow´s Penniman New Red Process
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1. Iron nitrate preparation
2. Iron oxide seed preparation (pressure reactor)
3. Penniman reaction (pigment growth)
Penniman Red Process – Basic Steps
Iron + Nitric acid Iron oxide seed + Nitric oxides (NOx)
Iron + Nitric acid Iron nitrate + Ammonium nitrate
Iron + Iron nitrate + Seed + Air Pigment + Nitric oxides (NOx)
3. Penniman-Reaction
Drying (and Milling)
RED PIGMENT
Filtration,Washing
1. Iron nitrate
Air
Steam
HNO3
2. Seed
Waste-water
HNO3Fe
NOx
Chinese producers use the Penniman Red Process for the production of Red FEO pigments
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IronIron
3. Penniman-Reaction
Drying (and Milling)
RED PIGMENT
Filtration,Washing
1. Iron nitrate
Air
Steam
HNO3
NOx
2. Seed
Waste-water
HNO3FePenniman Red Process – reaction principles
Fe
O
O
O2
Fe OO
SeedSeed
Fe2+
O-
NO3-
NO3-
O2
H+
Air
O-
H+
Fe2+
O2
NH4+NH4+
Step 1: Adsorption of Fe2+
Step 2: Oxidation
Step 3: Dissolving of iron
Step 1: Adsorption of Fe2+
Step 2: Oxidation
Step 3: Dissolving of iron
NN OO
Penniman Red – Growing of the pigment particle seed
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Major finding: In today´s standard Penniman Red process technology significant amounts of laughing gas are formed
Known to the industry:
Formation of toxic nitric oxides (NO, NO2) in the
Penniman Red process
NEW finding and not described yet:
Formation of laughing gas (N2O)
Significant amounts of laughing gas are formed in
the Penniman Red process which could not be
avoided by process optimizations
A small molecule, but a large impact on process
ON
O N
ONNO
Fe FeFe
Fe Fe
Fe
Fe Fe
Fe
FeFe
Step 1: Adsorption of nitrogen monoxide (NO)
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The waste gases from the process consist
of toxic nitric oxides (NO, NO2) and
laughing gas (N2O)
Laughing gas…
is a strong green house gas with a ~300 times higher
impact than carbon dioxide
is also a very potent ozone-depleting chemical
compound causing holes in the stratospheric ozone
layer, which protects the earth from UVB radiation
Waste gas emission
Today´s Penniman Red process offers a range of very attractive bright red pigments, but it is challenging due to environmental issues
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The waste water of the Penniman Red process contains ammonium nitrate, which is a very strong fertilizer
Discharging of ammonium nitrate into rivers and lakes leads to eutrophication – kills fish and causes shortages of drinking water
3. Penniman-Reaction
Drying (and Milling)
RED PIGMENT
Filtration,Washing
1. Iron nitrate
Air
Steam
HNO3
2. Seed
Waste-water
HNO3Fe
NOxN2O
Untreated waste water can cause eutrophication
Ammonium nitrate (NH4NO3) is an effective fertilizer and can cause algae blooms
Source: Sueddeutsche dpa
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Source: China environmental Report 2014, HCA Consulting China
China‘s environmental crisis
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China‘s focus on the reduction of NOx and ammonium nitrate
Source: China environmental Report 2014, HCA Consulting China2222
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Topics
Production processes for iron oxide red pigments1
4 Sustainable New Red pigments for the coatings market
2 Today´s Penniman Red Process
3 Tomorrow´s Penniman New Red Process
16
The Penniman red growth reaction requires large amounts of energy particularly in regard to steam stripping during the Penniman growth reaction
Due to process optimizations and special aeration techniques we were able to reduce the required amount of energy for the Penniman growth reaction by 80%
Energy savings Energy demand
[%]
Significant energy savings by efficient aeration technique in combination with process optimizations
Literature known NEW REDPenniman reaction Penniman reaction
80 % less energy
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1) Due to a higher solid content in our process steps, we reduced the required water amount considerably
2) The used water is subsequent purified in our state of the art water treatment plant by three methods:
o Sedimentation tanks
o Biological denitrification process
o Ultrafiltration and reverse osmosis (RO)
3) By reverse osmosis the sulfate-enriched water which is a valuable raw material, can be reused back in our process as a steering chemical
Recycling of process water
Na
SO4
Na
SO4
Na
Na
Na
SO4
Na
pressure
membrane
Purifiedwater
Principles of reverse osmosis
Up to 80% of the process water will be recycled and can be reused in our process
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Nitric oxides and laughing gas are formed in all three steps of the Penniman red process but especially in the seed formation and the Penniman reaction
Due to an efficient process control, we are able to reduce NOx and N2O emission significantly
Furthermore, our optimized process shows a steady stream of NOx emission which make the recycling scrubber system more efficient
Reduction of emissionsBefore
optimization
Optimized
process
Step one: Controlling and reduction of waste gas emission including laughing gas successfully
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Inorganic Pigments Group (IPG) will treat laughing gas, as well as toxic nitric oxides to naturally occurring air components
Despite having an efficient recycling scrubber system to recycle
the nitric acid, the waste gas still contains laughing gas (N2O)
and very small amounts of nitric oxides (NO/NO2)
A multi state catalytic converter will convert the gases into
naturally occurring nitrogen gas (N2), oxygen (O2) and water
(H2O)
CatalystNitrogen (N2)
Oxygen (O2)
Water (H2O)
Nitric oxides (NO/NO2)
and laughing gas (N2O)
Catalytic decomposition of NOx and laughing gas
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IPG´s New Penniman Red process will be the first, with exhaustive waste gas treatment, including laughing gas decomposition
CO2 impact
of average
Chinese
Penniman
Red
technology
Reduction
by laughing
gas treatment
Process energy savings
-71% of CO2 equiv
IPG´s process
Sa
vin
gs
of
88
%
of
CO
2
eq
uiv
ale
nts
pe
r to
n p
igm
en
t For the average Chinese
production of 1 ton Penniman
Red pigment, climate altering
gases with an impact of 25
tons of carbon dioxide
equivalents are formed.
Our New Penniman Red
Process will reduce the
formation of carbon dioxide
equivalents by 88% or 3 tons
of carbon dioxide equivalents
per 1 ton of Penniman Red
pigment.
-17% of CO2 equiv
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Topics
Production processes for iron oxide red pigments1
4 Sustainable New Red pigments for the coatings market
2 Today´s Penniman Red Process
3 Tomorrow´s Penniman New Red Process
22
LANXESS’ existing Laux Reds cover a very wide spectrum of red color shades with high milling stability and also are strong with bluish red pigment shades
Wide color spectrum for iron
oxide reds
High milling and heat stability
reds due to calcination
Strength in medium and bluish
red color shades
But, limitations of the light
yellowish color shades
Laux Reds
LANXESS Laux Reds
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Copperas Red shades cover a missing color space – however this production process is not used by LANXESS because of environmental issues
Color shade of Copperas Reds
(e.g. 1599D, 3098D) with
strengths on clean yellowish red
These red types cover the
missing color space to our
Bayferrox Red product range
However, Copperas production
process is seen by LANXESS as
environmentally unfriendly and is
therefore not used by LANXESS
Laux Reds
Copperas Reds
Laux vs. Copperas Reds
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Laux vs. Copperas vs. existing Penniman
LANXESS has chosen the Penniman Red process to bring bright New Reds similar to Copperas Reds to the market – our latest investment in Ningbo
Pigments produced by the
Penniman process have a very
clean color shade red with the
advantage of a light yellowish
color shade
The New Reds produced in
Ningbo will cover a part of the
Copperas as well as a part of
existing Penniman Red range
and are an extension of the Laux
color range
Laux Reds
Copperas Reds
Existing Penniman Reds
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LANXESS Inorganic Pigments – New Red
New Red color shades – a major finding in our trial production for the Penniman Reds showed that we will be able to produce even brighter red shades
New Red color shades - unknown
to today color space for iron oxide
Red pigments, opens the door for
new opportunities
All the pigments produced in the
new Ningbo plant will comply with
the Bayferrox quality standards
The high product requirements for
the Coatings industry will be fulfilled
The products will be produced in
the most sustainable way
New products and applications may
be possible for our customers
Laux Reds
Copperas RedsNew Red Shades
!
New Red from Ningbo
Existing Penniman Reds
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Summary
Nearly 50% of the todays global iron oxide red is produced in China and heavily pollutes
the environment.
LANXESS – Having 88 years in iron oxide production, IPG has the experience to optimize
the Penniman Red production to a real sustainable process.
New color shades of iron oxide reds could be achieved
The New Penniman Reds are an optimal extension for the well known Laux Red pigment
LANXESS - As a responsible partner for the paint industry, it is our duty to solve
existing environmental problems and also develop the best products for the
industry
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Dr. Volker SchneiderHead of Global Competence Center Paint
And
Dr. Waldemar CzaplikInorganic Pigments R & D
Many Thanks to the following
Acknowledgements
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Thank you for your attention!