new developments in foam production

New developments in foam production

XPS – co-blown CO2/ethanol

Waterblown PU Foams preliminary results

GIZ Proklima InternationalUNEP ECA Network Meeting

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11th May 2011, Belgrade

Bernhard Siegele, GIZ-Proklima

Projects funded by

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� Since the 1st January 2011 the GTZ changed it’s name to GIZ due

to a merger with:

� DED – Deutscher Entwichlungsdienst GmbH

� InWent – Internationale Weiterbildung und Entwicklung

GmbH

Content

� Introduction GIZ Proklima

� HCFC Phase out – low-GWP alternatives

� Future replacement blowing agents for HCFC

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� Future replacement blowing agents for HCFC

� PU Foam

� XPS Foam

� XPS conversion to CO2

� Waterblown tests Iran

� Concluding remarks

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HCFC phase-out and HFC phase down

� Montreal Protocol Obligation to phase out the use of HCFCs until 2030

� Proposals to phase-down the use of HFCs until 2030s

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0%

20%

40%

60%

80%

100%

2010 2020 2030 2040 2050

HFC-Phase down proposals

NAProposal

FSM Proposal

0%

20%

40%

60%

80%

100%

2010 2020 2030 2040 2050

HCFC Phase out

worldwide HFC-emissions projection till 2050

30

35

40

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0

5

10

15

20

25

2000 2005 2010 2015 2020 2025 2030 2035 2040 2045 2050

Gt

CO

2e

q

2050: 43,5% of

total CO2eq

emissions2010: 1,3% of total

CO2eq emissions

total CO2 emissions target in order to

achieve 450 ppm atmospheric

concentration levels (IPCC 3rd

Assessment Report)

HFC-emissions

ODP & GWP of selected foam blowing agents

Substance ODP GWP

CFC-11 1 4,680

HCFC-141b 0.11 713

HCFC-22 0.055 1,780

HFC 134a 0 1,410

HFC-152a 0 122

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HFC-227ea 0 3,140

HFC-245fa 0 1,020

HFC-365mfc 0 780

n-pentane 0 <25

iso-pentane 0 <25

c-pentane 0 <25

CO2 0 1

Future replacement blowing agents for HCFC

� The phase out of HCFC (141b) reopens the chapter of selection of blowing agent.

� There are several new developments which will require some years to mature and supply and costs will be the main issue

� Insulation is a must and in Europe buildings account for 40% of energy use* making it the largest Greenhouse gas emission source. So, insulation will

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use* making it the largest Greenhouse gas emission source. So, insulation will increase as it is an immediate method to reduce emissions.

� Most important seeing developments in EU, further efforts to improve the climate is that anything above a GWP > 150 will be intermediate , following the ongoing verification of the F-Gas Regulation;

� Health /Safety /Environment considerations have to be taken into account in the trade off for the replacement blowing agent. Whereby in particular waste management for rigid foam, like practiced with domestic refrigerators, will be a top issue.

*: Eurima Ecofys VII study 2007 #: Umweltbundsamt Oct 2008

Future replacement blowing agents for HCFC

Introduction – Waste Management� The GIZ is implementing in Brazil, the line will go on-line 2nd quarter of

2011, a recovery, recycling & destruction plant for domestic refrigerators.

� This is widely applied in the EU and is going to be implemented in the USA

under the supervision of the EPA.

� For understanding the trend, Austria-Denmark-Switzerland already banned

HFC’s in foams. HFC’s are considered Hazardous Waste.

If refrigerants are easily recovered, vacuum pump and cylinder. The recovery

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� If refrigerants are easily recovered, vacuum pump and cylinder. The recovery

of CFC-HCFC-HFC inside foams requires complicated and expensive plants. A

management of collection and transport of large foam products and

incineration plants.

HCFC and HFC containingdismantled insulation boards

are Hazardous Waste*) !

*: presentation F. Leutgeb, Bauxund, workshop XPS 9-11 Nov 2009 Beijing: Waste Inventory Ordinance 2003, Enforcement of CD 75/442/EEC on waste:

A 6 m sandwich panel of 50 mm

contains >500 grams of blowing

agent!

Blowing agent principle

� A blowing agent helps the nucleation process and creates a foam composed of cells (open or closed)

� In these cells (closed) the blowing agent is enclosed and contributes to the thermal conductivity of the foam.

� This cell gas is then composed of a mixture of

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� This cell gas is then composed of a mixture of air and blowing agent and together with the solid PU material provides the overall thermal conductivity.

� Long term properties are determined by the remaining content of blowing agent inside the cells as diffusion out of the cells occurs. This is more dominant with XPS as no barriers or facings are used than with PU where with sandwich panels a metal facing provides a barrier.

Blowing agent principle

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� The gas in liquid state is ejected together with the foam and during the transformation in gaseous state creates gas bubbles (important: temperature, enclosure pressure).

Thermal conductivity

� λFoam = λP + λG + λR+ λC

� λP = heat conduction of the cell framework ++++� λG = heat conduction of the cell gas ++++� λR = heat transfer through radiation +

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� λR = heat transfer through radiation +� λC = heat transfer through convection +

� The cell gas is one of the contributing factors of the overall foam λ but not the determining factor.

� You choose the foaming system not blowing agent !

Thermal conductivity

� Factors that influence the λ Foam� Design of the product� Cell size, distribution and orientation� Composition of the cell gas

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� Composition of the cell gas� Aging of the foam� Density of the foam, equipment� Storage, temperature control raw materials� Etc.Only when optimised conditions are met good results

are achieved, if not : invest in low cost blowing agents!

Insulation properties

� As we already noted thermal conductivity (λ W*m/K) is one of the properties, although important but not determinant. The reason being that Architect, Engineers work with R or the reverse U-value to determine the insulation properties of a building.

This means that with increase

of thermal conductivity the

12

14

chan

ge (

mm

)

Influence of variation of thermal conductivity on thickness of a 1 m2 50 or 100 mm board

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of thermal conductivity the

panel thickness increases.

These changes are however

little. 0

2

4

6

8

10

0.00 1.00 2.00 3.00 4.00

Thi

ckne

ss

chan

ge (

mm

)

Variation of thermal conductivity (mW/m.K)

50 mm 1m2 panel

100 mm 1m2 panel

The compensation of a loss of insulation through increase of the thickness is a

valid environment sustainable solution for the long term. Therefore that the

GIZ is a promoter of Hydrocarbons or waterblown solutions in PU and XPS

foams.

Blowing agent overview – PU foams

U-HFC Fluor basedNew Generation

Expensive – SpecialAvailable in 2-3 years

Hydrocarbons (Pentane)More then 10 years

development

Methyl typesRenaissance of „old“ blowing

agentsAlso Flammable !

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developmentUsed by >90% Appliance

and Sandwich panelCheap i.e. Low foam costs!

Higher equipment costs

HFCToo High GWP!

Intermediate solutionExpensive

EU F-gas GWP < 150!!

Water blownImmediate use

No need of mixing or special equipment

Slightly lower λ Foam HC<=Foam

cost<HFC<HFO

Blowing agent overview - PU

U-HFC 2nd CFC-11 HFCU-HFC 1st** HCFC 141b HC Methyl CO2

Molar weight >135 137.4 >134 114.2 116.9 70 70 44

Boiling point °C 15/25 23.7 -16/+40 -19/-30 32.1 25/50 30/40 -139

GWP ?? 4750 >1000 <150 725 <15 ?? 1

ODP 0 1 0 0 0.11 0 0 0

LEL/UEL Yes No Yes/No Yes Yes Yes Yes No

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LEL/UEL Yes No Yes/No Yes Yes Yes Yes No

λ Foam = -1/-2 +0/+1 = reference +1/+2 +1/+2 +2/+3

Costs US$/kg >10-20 X >8 >10-20 >3 >1 >1* <1

Blowing agent required pbw wrt 141b***

+4/+5 +3/+4 +3 = Reference -8 -8N.A.

Co-blown

* additional required License costs, status 3rd quarter 2010 for methylformate** low boiling u-HFC suitable for XPS*** based on molar weight calculation, pbw on 100 pbw polyol, does not consider water co-blown

Note: boiling point < ambient temperature: requires special equipmenta blowing agent with a LEL/UEL requires ventilation, sensors and ATEX

Blowing agent overview - XPS

� The properties of XPS derive from its use in the construction sector where the XPS is used as insulation material.

� Therefore compliance with the requirements is a must as the lifetime of buildings are decades, 50 years considered in the EU and the XPS insulation is part of the building.

� Several players play a role in the use of XPS as well as need to rely on the long term properties.

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XPS blowing agent development

� Development

HCFC 142bODP = 0,06GWP = 1600

HFC 134a / 152aODP = 0GWP = 140 / 1430

CO2ODP = 0, GWP = 1

ODP: ozone depletion potential

GWP: global warming potential

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1960 1970 1980 1990 2000 2010

Methyl Chloride

CFC 12ODP = 1, GWP = 7500

GWP = 1600

CFC- ban, 1995:EU Reg 3093/944 HCFC-ban, 2002:

EU Reg 2037/2000

HFC BAN Switzerland, Austria, Denmark ......

HCFC-ban, 2010-Jan-1, USA

� Typical blowing agents (BLA) used are:

Common used in Art.5 Used in Europe/US (HCFC banned since 2002–2010)

HCFC’s� HCFC 22� HCFC 142 b� HCFC 22/142 b

HFC’sHFC 134 a / 152a blendsHFC 152a + aceton

HC’s (flammable)• Isobutane

XPS Technology options

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HFC’s� HFC 134 a

• Isobutane• LPG (mixture of isobutane+Propane+N-butane)

CO2• CO2 + organic solvents e.g. ethanol, DME• 100% CO2 (Patented)

Other•Vacuum technology (Patented)

•New – u-HFC

At the moment the alternatives to HCFC used can be summarized as follows:

Country Blowing agent* R&D

EU CO2+organic solventHFC 152a

U-HFC

EU + USA HFC 134a U-HFC

Japan + EU Isobutane

XPS Technology options

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Note that all the foams without 134a have similar “R value” and HFC-134a has an improved value. In the US HFC-134a is used because of the construction Standard. HFC-152a is still used although it does not provide any benefit, for it’s flammable but older production lines can be used.

There are indications that the future replacement for 134a could be an u-HFC. Still there are no commercial applications, developments are expected.

*: practically all options are mixtures, pure HFC a re normally not used. HFC are named as main blowing agent only.

China: Converting XPS foam production from F-gases to climate-friendly CO2 technology

The purpose of this pilot project is to install a new production line for XPS foam at the site of the company Beijing Beipeng New Building Materials Co. Ltd near Beijing to demonstrate the use of environmentally friendly CO2 as blowing agent instead of the currently used fluorinated gases. This insulation foam is based on European standards and adapted to Chinese conditions and regulations.

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regulations.The project avoids ca. 1.6 million tons CO2eq direct emissions through the

permanent replacement of the blowing agents HCFC-142b and HCFC-22, based on an annual production of 4,320 tons XPS insulation foam.

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XPS conversion from 142b/22 –CO2+Ethanol

• The GIZ Proklima together with MEP/FECO (PRC) financed by the BMU (Bundesministerium für Umwelt, Naturschutz und Reaktorsicherheit) have converted an XPS industry from the use of 142b/22 to CO2+Ethanol.

• This Project started in March 2009 (PO) and

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• This Project started in March 2009 (PO) and commissioning was finalised in May 2010.

• Up to 60 mm boards were produced without any HCFC or HFC with good grade quality considering also that recycled material was also used.

• The 50 mm boards which were tested in the laboratories of BASF Germany and showed a thermal conductivity of 33 mW (10°C), 400 Kpa compression strength (10%) as well passed the EU fire test, complying with EU standards.

XPS conversion from 142b/22 –CO2+Ethanol

• Following the successful commissioning the company is experimenting new processing methods, materials and products.

• Follow-up projects are on-going with two different Universities with the scope of increasing the know-how, development of new raw materials and providing training capabilities to the Industry.

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raw materials and providing training capabilities to the Industry.• The company has in the period of May 2010 - March 2011

produced 1,900 tons XPS, this resulted for the period of 2010 in a reduction of about 600* ktCO2eq and 21 ODP T.

• XPS lines which work 24hr, 7 days a week have a high consumption and a cost comparison between the blowing agents used** and CO2 made the beneficiary decide, invest and further develop this technology.

*: taken into consideration that for higher thicknesses HFC-152a has been used**: app. 140 Ton CO2+ethanol +152a versus 350 T 142b/22 for 2010

XPS Machinery conversion remarks

The benchmark is not easy when considering the optimal solutions which can be provided in A2 countries with the realities in A5 countries.

Low technology equipment will have limited possibility to succeed with a change of blowing agent considering the difficulty to achieve the standards.

A5 A5 A2

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No comparison possible between existing and alternative blowing agent

Benchmark available for comparison with alternative blowing agent

A5 A5 A2

XPS sector China

� Strong growth in the sector (ca. 20% p.a.) due to new energy-efficiency regulations for buildings

� Based on successful technology demonstration and adaptation to local conditions this technology

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and adaptation to local conditions this technology was defined as preferred option in the sector plan (HPMP)

� 80% of ca 500 companies in the sector to be converted in the next years:� 40-50 production lines till 2015

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Waterblown foam test Iran

� The first question to ask why Waterblown for a commercial refrigeration company?

� The GIZ as lead agency for the foam sector under the NPP and HPMP has seen that there are many small companies with a mean consumption of less then 7 MT HCFC for which a conversion is not feasible. Because they are second conversions, contribution for the phase-out is not sufficient and

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conversions, contribution for the phase-out is not sufficient and the alternative: Hydrocarbon (Pentane) is not feasible because:� The companies are producing many different sizes� Foaming know-how is not available� Their focus is mechanical workmanship and not foam or

refrigeration� The consumption is too low for the investment component

as well as the companies cannot contribute


� The second important question to ask: How important is the foam?

� Commercial refrigerators in supermarkets, shops are partially open, vertical display cabinets open top refrigerators/freezers therefore the foam acts as insulator but equally important are the mechanical properties.

� The largest source of heat leak are actually the openings and

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� The largest source of heat leak are actually the openings and doors!

� The models used are in general larger than domestic refrigerators but at the same time the number of models produced are often tailor made. The in-liner is of steel and when used the doors are window type.

� Therefore the companies when foaming are focusing on the mechanical more then insulation properties .


Scope of our tests?� Together with BASF (Lemförde) tests are performed which will

be finalised in 2-3 months time with the scope of:� Verifying the state of the art business as usual (BAU)� Optimising the foaming with HCFC to show to the

beneficiary the potential benefit

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� Introducing waterblown foam� This BAU status is important to understand which benefits can

be achieved within the context of a conversion and to which extend it needs to be implemented.

� For this purpose we have procured a waterblown foam and foamed several cabinets which will be tested in Germany at an independent institute for measurement of the reverse heat leak test and mechanical properties at BASF.


� Expectations commercial refrigeration companies� Before we started and discussed with BASF our view was that

most of the companies have a low level of know-how with regard to foaming.

� Due to the large amount of models produced in small series or single pieces the foaming part is often challenging for the producers.

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producers.� The proper use of the foaming equipment and knowledge

required for using blowing agents is an issue.� The substitution with a waterblown system will provide similar

foam properties as with HCFC-141b. As well a substantial simplification for the producer with regard to foaming.

� As it is quite a difference of using a system with incorporated blowing agent properties as a third component, i.e. blowing agent.


� Preliminary results during the foaming already confirmed several expectations:Machine settings�Foaming pressure too high ≈ 170 bar

�Temperature of raw materials too low ≈ 18°C�Factory hall and therefore non preheated mould too cold 15°C

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Foam�Ratio between polyol and Isocyanate had to be corrected�Too much foam has been used and was reduced�Drums with Polyol and premixed 141b not stirred (in summer a common mistake is also to underestimate the evaporation!)

Operators�Executers with no background knowledge of foam

Waterblown foam test Iran� Let the company produce the refrigerators as they normally do, in order to

establish the BAU status.

� Subsequently re-adjusted the foaming machine and produced an optimized

141b cabinet.

� On the basis of this data foamed with the waterblown system whereby

excellent adhesion was accomplished with a heated and non heated mould.

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� Preliminary conclusions� The manufacture of commercial refrigerators is challenging

with regard to foams which will lead to underperformance of the foams. The use of a blowing agent is not an insurance for properties but proper foam is.

� Confident that the waterblown foamed refrigerators will present the same performance as 141b.

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present the same performance as 141b. � Awaiting the results of the laboratories in order to provide

a more complete picture of the results. But the foamed units are in transit and laboratory tests will be made in the coming weeks. Then also the refrigeration system will be reviewed.

Remarks to the PU - blowing agent selection

� Integral foams in the EU-USA-Japan are nearly 100% waterblown (FSK). Any blowing agent used will be released; therefore a loss from environmental as well as cost perspective. Any new blowing agent will need to be approved and excempt of VOC (Methylformate e.g. is not exempted in the EU). Best solution are HC when further density reduction is wanted or waterblown systems.

� Domestic refrigeration is practically 100% HC, the USA is also moving

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� Domestic refrigeration is practically 100% HC, the USA is also moving into this direction because for A+++ other techniques are required.

� Sandwich panels are 100% Hydrocarbon in the EU-USA-Japan, discontinuous panels are moving into this direction for replacement of HFC’s.

� U-HFC are showing good properties on laboratory scale but will be considerably more expensive then HFC’s, available on large scale in 2-3 years therefore for the first phase not an option for Art.5 countries.

�

#: Caleb management services Ltd. Determination of comparative HCFC and HFC emission profiles for the foam and refrigeration

sectors until 2015 (Foam projections) Part 2, 07/04/04

Remarks to the XPS - blowing agent selection

� Most of the producers use a mixture of blowing agents because of

constraints on processing and cost.

� The only “beneficial” blowing agent with respect to thermal

conductivity is HFC-134a which has however a non acceptable GWP

and is already banned in several EU countries.

� HFC-152a does not provide any benefits, is flammable, will be emitted

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� HFC-152a does not provide any benefits, is flammable, will be emitted

100%, requires safety measures to be taken and will although the

GWP is about 150 have a negative balance.

� U-HFC could be a replacement for some A2 countries where high-end

XPS foams are required. The costs for A5 countries will make it a not

likely alternative.

� CO2 + organic solvent is at the moment the best solution as the

blowing agents are available in every country and are the less

expensive solution.

Blowing agent selection� The major challenge during the HCFC phase out is the availability of

HCFC when replacements are more costly.

� Secondly the application know-how of the beneficiary as processes

will need to change. The majority of HCFC141b users are small

companies who do not have sufficient R&D in-house.

� For XPS besides PRC, it is an emerging industry but with high

consumption without adequate constraint measures. Countries

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consumption without adequate constraint measures. Countries

where the industry still is under establishment should ban 142b/22

immediately not to substitute the phase-out of 141b with 142b/22.

� The base materials Polyol (PU) and polystyrene (XPS) must be

suitable for the use with a specific blowing agent. Therefore,

verification with the major raw material suppliers in your country is

important. Interchange of know-how through associations and

industry.

� The speed with which Industry can exchange and adapt is often underestimated but guidance is required.

Barriers to low-GWP refrigerantsGIZ Proklima activities to help overcome barriers

• Example: Comprehensive guidance on low-GWP technology

― Translated/translating into many languages

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Conclusions

� Increase in foam production expected in the region due to different policies (climate change, energy efficiency, buildings efficiency)

� Important to promote ‘right’ choice from the

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� Important to promote ‘right’ choice from the beginning – low-GWP alternatives available for all company sizes (including MSMEs)

� Interested in cooperation to demonstrate new technologies in foam production in ECA region

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Thank you!

Contact:

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Proklima InternationalDeutsche Gesellschaft für Technische Zusammenarbeit (GTZ) GmbHDag-Hammarskjöld-Weg1-565760 Eschborn, Germany

Email: [email protected]: www.gtz.de/proklima

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