International Seminar

Organized by:

Ministério do Meio Ambiente-Brazil, UNDP and Ministerio Dell’ Ambiente-Italy

Governement

Alternatives to HCFCs in Foams Sector - Technology Options and Equipment

Chapecó-Santa Catarina - Brazil - July 2014

Hydrocarbons and water as blowing agents to replace HCFC141b

in Polyurethane Rigid Foams

Paulo Altoe’ - Product Technology Manager - Dow Brasil S.A paltoe@dow.com

Rodnei Abe – Product Technology Manager - Dow Brasil S.A rmabe@dow.com

Marcelo Fiszner – Marketing/R&D Director - Dow Latin America mfiszner@dow.com

Blowing Agents Evolution

• The evolution of BAs technologies, driven by regulation and market trends moved far from 1st

generation BAs (CFCs)

• Uses of Gen 1 and 2 is regulated by Montreal protocol (Ozone Depletion Potential ODP)

• HFCs � high GWP substances are currently not regulated. However market trends indicate that

they will be probably in the future

• On top of Hydrocarbons (HC) and water, HFO ����Gen 4, Hydrofluorolefines will represent a viable

Low GWP alternative to HFCs

Gen1 Gen 2 Gen 3 Gen 4

High ODP

High GWP

Low ODP

High GWP

Zero ODP

High GWP

Zero ODP

Low GWP

CFC-11 HCFC-141b HFC 134aHFC 245fa

HFC365mfc/227ea

HFO

HC and Water

Blowing Agents - Properties

Not commercially available

Table 1

Performance Overview - Different Blowing Agent Technologies

• Zero ODP and Low GWP � Water, Hydrocarbons , Formic Acid, Methylal , Methyl Formate and HFOs

• Zero ODP ���� HFC-134a, HFC365/227ea , HFC245fa

Blowing Agents - Selection by Performance and Application

• The general properties reported in Table 2 can be considered as a guidance for the

choice of the right blowing agent for each application

• In fact each application will have its own peculiarity and set of most important

properties, and this will guide the choice

• For example, for those applications driven by thermal insulation, a full water blown

solution will not be the most effective one

HCFC141b Elimination - Blowing Agents Alternatives

Laboratory data also validated in production

HCFC141b Elimination – BA Alternatives

Applications

• Panels : Continuous and Discontinuous

• Walk-in Cold Rooms

• Blocks; Commercial Refrigeration

• Insulated Trucks, Reefers

• Pipes, Tanks

• Thermal wares, boilers

• Spray

• …

HCFC141b Eliminations – Criteria for Blowing Agent Selection

Blowing Agent versus Application

• Environment & Sustainability

• Quantity of Process Foam (Year)

• Foam Cost

• Applied Density

• Processing

• Energy Efficiency (lambda)

• Blowing Agent Flash Point

• Investment - Machinery

• Investment - Molds

• Temperature Control/ Sensors

• Foam competiveness vs competition

• …

-Hydrocarbons are widely used with advantages of process, cost and thermal insulation

-Water blown systems are used in applications where thermal insulation is not a major requirement.

-Proper temperature control is required to avoid poor adherence in water blown systems

Discontinuous Panels – DCP

They are mainly used in cold chain, as commercial and industrial cold store

panels, and in costruction applications.

Main requirements are:

• Thermal insulation

• Fast productivity/cost

• Aesthetics

• Fire properties (both fire rated and not fire rated options are available)

HFCs, for instance HFC134a/AF, is normally used in developed countries

Main requirements are:

• Fast productivity/cost

• Thermal insulation

• Aesthetics

• Fire properties (both fire rated and not fire rated options are available)

Discontinuous Panels – DBL : Double Band Lamination

-Hydrocarbons are massively applied and represent the best option for HCFC141b elimination

-Water blown systems are used in sliding shutters and sectional doors applications where

foam k-factor is not a major requirement

HFCs are much less diffused in the market. They are used for customers sensitive to safety aspects

Main requirements :

• Thermal Insulation

• Good dimensional stability

Spray

Water blown systems fit very well to eliminate HCFC141b in spray applications

Hydrocarbons are not recommended due to risks of flammability in spray applications

HFCs, are recommended

Different fabrication processes: Pipe-in-Pipe discontinuous; continuous pouring and spray.

Main requirements :

• Mechanical resistance

• Max operating temperature

• Thermal Insulation

Pipes

-Hydrocarbons represent a viable alternative for foam production with good performance

-Water blown systems are recommended where foam insulation is not a fundamental

requirement

HFCs, are suitable alternatives for HCFC141b elimination

Main requirements:

• Thermal Insulation

• Good processing and low cost

Portable Coolers and Boilers

-Systems expanded with H2O are applicable. Temperature control is recommended for good

adhesion.

-Hydrocarbons represent a viable alternative due to foam properties and competitive cost, but

requires high investment.

HFCs, feasible for these applications

Main requirements :

• Thermal insulation

• High productivity /foam cost

Commercial Refrigeration

- Systems expanded with H2O are applicable. Low energy efficiency of water blown implies

additional costs in refrigeration systems.

- Hydrocarbons would be the best option versus volume of foam produced that could justify high

investments

HFCs, widely used in this application

• DCP Technology is used to produce panels for different segments in Cold Chain Industry,

e.g. Walk-in cold rooms, industrial cold stores, refrigerated transportation.

• Diferent injection technolgies are used: single injection point; lance withdrawal; open lid

and more sophisticated like VAI: Vacuum Assisted Injection

DCP – PUR - Hydrocarbon Technology in Cold Chain

* lower density=DCP for cold rooms, higher density=refrigerated trucks and sea containers

- Hydrocarbons blown systems have a wide range of properties, depending on the specific

application and foaming technology

- Typical Data: Lambda 21-23 mW / mK Density @ 24C and 36-60 kg/m3 *

• Besides PUR Technolgoy, Polyisocyanurates � PIR are used when superior fire

resistance performance is required

- Similarly, systems expanded with hydrocarbons have a wide range of properties

depending on the specific application and foaming technology

- Typical data of PIR : Lambda 22-24 mW/mk @24C and Density 40-45 kg/m3

DCP – PIR - Hydrocarbon Technology in Cold Chain

Hydrocarbons as alternative to HCFC 141b

• Validated technology for more than 20 years that provides high performance foams with

very competitive cost

• Requires high production foam volume to justify heavy investment for HC conversion

• Can be used in practically all applications (except spray )

H2O as alternative to HCFC 141b

• Recommended where thermal insulation is not a important requirement

• Foam cost is very competitive

• Higher applied foam density represents small incremental cost

• Requires strict range of temperature control of molds to improve foam adhesion that is

lower compared to other technologies

• Applications where foams are sealed in the structures will sustain thermal insulation with

very minor deterioration along life of equipment

General Comments

• Founded in 1987 by Herbert H. Dow in Midland, Michigan – USA

• Supplies a broad range of products and services to customers in approximately 160

countries

• More than 5.000 products manufactured at 188 sites in 35 countries

• Employs 50.000 employees globally

• Revenue of approximately US$ 60 billion in 2012

The Dow Chemical Co

• Dow has been active in manufacturing and R & D of PU foams for many years. It Is fully

committed to helping its customers and the industry to find best suitable solution to

meet their requirements in technology, processing and performance of materials

• Due to changes in the requirements of efficiency and blowing agents, Dow focused on

development of new formulations and innovative technologies capable to meeting

market needs and complying with all national and international laws and regulations

• Dow supplies a wide range of rigid polyurethane systems developed based on

hydrocarbons, water, and other innovative blowing agents

• The global reach of Dow combined with strong local presence enables a great proximity

to the base of our customers to deliver innovative solutions with quick response to the

market.

The Dow Chemical Co

Acknowledgment s

*Cecilia Girotti – Sr. R&D Chemist

*Giuseppe Vairo – Global Technology Leader

**Leo Bian- Energy Efficiency Technology Leader

**Si-Ho Lee – TS&D Leader

*Dow Italy

**Dow Asia Pacific