impact™ technology a greener polyether process -...

Polyurethanes

IMPACT™ TechnologyA Greener Polyether Process

Jack ReeseKen McDanielRobert LenahanRobert GastingerMark Morrison

Polyurethanes

Presentation Overview

Introduction to Polyether Polyol Market and Applications

Polyether Polyols Chemistry

IMPACT™ Technology – Catalyst and Process

A Greener Polyether Process Technology

Summary

Polyurethanes

Introduction to Polyether Polyols

Main Application Area for IMPACT™ Technology is Polyether Polyols for Polyurethanes.

Lower Molecular Weight (<10,000 Daltons) Polymers with Terminal Hydroxyl Groups.

Starters for Polyols are Typically Propylene Glycol, Glycerin, Sorbitol, etc.

Formed by the Catalytic Reaction of a Starting Polyol with an Epoxide Containing Monomer.

Other Application Areas for Alkoxylation Technology include Surfactants and various Functional Fluids.

Polyurethanes

Polyurethanes

RN OH

OR'

Polyether Polyols

Long Chainn > 8;

Functionality = 2 - 6

Cat

alys

tB

low

ing

Age

nt

Isocyanates

MDI NCOOCN

TDI

CH3NCO

NCO

Polyether Polyol Use in Polyurethanes

Polyether Polyols:

~ 40% of Polyurethane

~ 350 Different Varieties

Determine Unique Properties

Add

itive

s

Short Chainn < 8;

Functionality = 2 - 8

OHOO

n

HO OO

n

OO

HO

n

Polyurethanes

Fore

cast

0

2

4

6

8

10

12

14

16

201020051985198019751970 1995 20001990

2008:11.6 mT

(in mT)

PolyurethanesWorld Consumption 1970 - 2010

Polyether Consumption ~ 4.6 mT or 10.2 billion lbs/yr

Steady growth at 4% (average) per year

Polyurethanes

Rigid Foam 25,5%(Construction,

Insulation

Adhesives andSealants 5,5%

Elastomers 5,5%

Others 18,5%(e.g. TPU, Shoes,RIM, Fibers)

Total: 11.6 Mio T

Source: Marketing-Dienste Dreger:div. professional articel, Plastics 10-2008BMS expansion and estimate

Coatings 2,5%

Molded Foam 11,0%(Automotive,Furniture)

PolyurethanesWorld Consumption by Application 2008

Polyurethanes

Traditional Polyether Process Chemistry

Polyether Polyols are made by ring opening polymerization of an epoxide group onto a starter alcohol.

Main catalyst for the last 50 years is KOH.

StarterGlycerin as example R = CH2 for Propylene Oxide (PO)

R = H for Ethylene Oxide (EO)

+KOHOH

OH OH H2C CH

R

O

Polyurethanes


Polyether Polyols are made by ring opening polymerization of an epoxide group onto a starter alcohol.

Main catalyst for the last 50 years is KOH.

+OH

OH O- K+

OHOH O

O-

CH3

K+

Polymerizate or Crude Polyol

H2C CH

R

O

Polyurethanes


OHOH O

O-

CH3

K+

Polymerizate or Crude Polyol

Contains between 0.2 to 0.4% KOH

PO / EO PO / EO

OO O

PO PO...

PO PO... PO PO...HO O-

...

...

OH

K+

Polyurethanes


Crude Polyol with 0.2 to 0.4% KOH

OO O

PO PO...

PO PO... PO PO...

OH

HO O-K+

Work-up for K+ Removal

Neutralization

Distillation

Solvent Recovery

Purification

+ H2SO4

+ H2O

-K2SO4

-H2O

O

O O

PO PO...

PO PO... PO PO...HO OH

OH

Final Refined Polyether Polyol

Containing less than 10 ppm K+

Polyurethanes

KOH Technology

Advantages– Inexpensive catalyst.– Wide range of products / Industry standard.– Narrow molecular weight distribution.

Disadvantages– Long reaction times.– Need to remove catalyst (multi-step, energy intensive).– Side reaction that reduces functionality at higher MW.

K+ OH Allyl AlcoholIsomerizationPO

OH

Allyl Alcohol

OH+ n PO / EO

Monol or unsaturation

K+

n

H2C C

O

HCH3

Polyurethanes

Double Metal Cyanide (DMC) Catalysts Zinc Hexacyanocobaltate, originally with glyme as ligand.

Invented in 1964 by General Tire.

Advantages of glyme DMC catalyst over KOH:– Lower by-product formation (50 – 70% reduction).– Faster (shorter cycle times).

Disadvantages of glyme DMC catalyst over KOH:– Cost (Much more expensive than KOH).– Difficult DMC catalyst removal step.

ZnCl2 + K3[Co(CN)6] Zn3[Co(CN)6]2.8 H2O.Crystalline solid

Ligand = GlymeZn3[Co(CN)6]2. ZnX. GlymeAmorphous/Crystalline

Catalysts

Polyurethanes

IMPACT™ CatalystDeveloped in mid-1990s by ARCO Chemical (now part of Bayer).

Order of magnitude improvement in activity over glyme catalyst.– Low catalyst levels possible – no catalyst removal required.

KOH IMPACT™

Rea

ctiv

ity

~ 1000x more Reactive than KOH

More selective – little to no by-product

Faster Reactivity, Increased Selectivity, Simpler Process:The Key to a Greener Technology

Polyurethanes

IMPACT™ Catalyst

Key invention was the novel combination of two ligands.

Amorphous catalyst structure.

XRD of IMPACT™

Amorphous/Crystalline Catalyst

R 1O Zn

O R 2

Cl

CN

H

Co C NCN

NCNC CN

3 -

M atrix

Zn 3

2

ZnCl2 + K3[Co(CN)6]

Ligand 2Ligand 1

Zn3[Co(CN)6]2• ZnClY(OH)Z•L1•L2 • H2O

Lin

(Cou

nts)

0

500

1000

1500

2000

2500

3000

3500

2-Theta - Scale5 50

Zinc HexacyanocobaltateIMPACT 3

Lin

(Cou

nts)

0

500

1000

1500

2000

2500

3000

3500

2-Theta - Scale5 50

Zinc HexacyanocobaltateIMPACT™

Polyurethanes

Zn3[Co(CN)6]2• ZnClY(OH)Z•L1•L2•wH2O

InactivePO -H2O

Low Molecular WeightStarter

PG, Glycerin Catalyst Inhibited

Reversible

High Molecular WeightStarter

Very Active CatalystHeterogeneous

Particle Size Decreases

Industrial Challenge: Develop efficient process technology to use lowmolecular weight starters (Gly or PG) directly.

IMPACT™ Characteristics

Catalyst undergoes activation in the

presence of starter and oxide – MW

dependent.

PO -H2O

Polyurethanes

IMPACT™ Process TechnologyA more efficient process was required for commercial success.

Solution was provided in an inventive process named Continuous Addition of Starter or CAOS.

low MW polyol heel

PO / EO PO / EO Gly / PG

Semi-batch process: CAOS process:

Starter: 1000 MW made via IMPACT™

Starter: 700 MW made via KOH

Product: 3000 MW Product: 3000 MW

IMPACT™ Catalyst

CAOS is a more efficient process technology that eliminates the need for KOH products as starters.

Polyurethanes

CAOS – Taking Advantage of Unique Kinetics

IMPACT™ Catalyst can tolerate low levels of glycerin or propylene glycol.

Conventional polymer kinetics predict broad polydispersity.

Example with 500 MW and 2000 MW as starter mix.

KOH Catalysis as predicted by conventional polymer kinetics, Flory

500

2000

750

2250

1000

2500

2000

3500

Polyurethanes

CAOS – Taking Advantage of Unique Kinetics

Example with 500 MW and 2000 MW as starter mix.

KOH Catalysis as predicted by conventional polymer kinetics, Flory

500

2000

750

2250

1000

2500

2000

3500

IMPACT™ Catalysis

500

2000

1000

2000

1500

2000

2000

2000

“Catch-up Kinetics”

Polyurethanes

“Catch-up” Kinetics Demonstration

Molecular Weight

POAddition

Wei

ght F

ract

ion

3600 2000 800 400MW:

0%

26%

36%

45%

65%

100%

POAdded

Starting Reactor Contents

Lower Molecular Weight Species React Preferentially Providing a Narrow Polydispersity with Continuous Addition of Starter Technology.

Polyurethanes

Highly active catalyst.

Ability to add low molecular weight starter during monomer feed.

Utilizing Unique Kinetics to Optimize the Process

Ideal conditions for a continuous reactor system

Polyurethanes

StarterEO, POCatalyst

Reactor - CSTR Cook out – PFR / CSTR



Tank Farm

IMPACT™ Continuous Technology

Highly active catalyst.

Ability to add low molecular weight starter during monomer feed.

Utilizing Unique Kinetics to Optimize the Process

0

50000

100000

150000

200000

250000

300000

350000

400000

100 1000 10000 100000

log(M)

GPC-

Sign

al0

1000000

2000000

3000000

4000000

5000000

6000000

7000000

8000000

9000000

IMPACTKOH

Continuous Product

Ideal conditions for a continuous reactor system

Theoretical Distributions

Polyurethanes

Polyether Process Technology ComparisonKOH, Semi-Batch

IMPACT™, ContinuousSaving Areas:

• Energy / Steam

• Waste


Tank Farm

Salt

ReactorNeutralization

or Solvent Addition Distillation / Solvent Recovery

Purification

Quality check

EO, PO

Starter Reactor

Solvent / Water





Tank Farm

Polyurethanes

IMPACT™ Technology – Energy SavingsKOH, Semi-Batch


Tank Farm

Salt



Purification

Quality check

EO, PO

Starter Reactor

Solvent / Water


Tank Farm

Salt



Purification

Quality check

EO, PO

Starter Reactor

Solvent / Water


Reactor

EO, PO

Starter Reactor


Reactor

EO, PO

Starter Reactor

Energy Savings:

• Eliminate heat up and cool down for every batch.

Reduces steam and cooling water.

Polyurethanes

KOH, Semi-BatchStarterEO, POCatalyst

Tank Farm

Salt



Purification

Quality check

EO, PO

Starter Reactor

Solvent / Water


Tank Farm

Salt



Purification

Quality check

EO, PO

Starter Reactor

Solvent / Water

Solvent / Water

Distillation / Solvent Recovery

Solvent / WaterEnergy Savings:

• Eliminate distillation of water and/or solvent recovery.

IMPACT™ Technology – Energy Savings

Polyurethanes

IMPACT™, Continuous


Reactor -CSTR Cook out –PFR / CSTR


Reactor -CSTR Cook out –PFR / CSTR


Tank Farm

Salt



Purification

Quality check

EO, PO

Starter Reactor

Solvent / Water


Tank Farm

Salt



Purification

Quality check

EO, PO

Starter Reactor

Solvent / WaterKOH, Semi-Batch

Energy Savings:

• Steam and cooling water for batch process.

• Eliminate distillation of water and/or solvent recovery.

Reductions – Steam = 99%, Electricity = 75% and Cooling Water = 88%

• Potential to generate steam w/continuous process.

IMPACT™ Technology – Energy Savings

Polyurethanes

KOH, Semi-Batch

Solvent / Water

Waste Reduction:

• No aqueous waste generated from solvent removal and recovery.


Tank Farm

Salt



Purification

Quality check

EO, PO

Starter Reactor

Solvent / Water


Tank Farm

Salt



Purification

Quality check

EO, PO

Starter Reactor

Solvent / Water

Salt

• No solid waste generated from catalyst removal.

Reductions – Solid waste = 100%, Aqueous waste = 98%

IMPACT™ Technology – Waste Reduction

Polyurethanes

IMPACT™ Technology – Green HighlightsCase Study: Channelview, Texas facility – one KOH reactor and one continuous reactor making similar products.

Easy conversion of existing KOH reactor to provide low cost capacity increase while reducing process complexity.

Very consistent product quality – reliable on-line monitoring possible.

Little to no by-product formation – lower volatile organic compounds (VOCs) in product.

Lower un-reacted oxide inventory in the reactor during the reaction further reducing process safety risk.

Wastewater reduction of 75 million pounds per year.

Reduction of total energy consumption by 80 percent – this equates to a yearly reduction of 54 million pounds of CO2.

Polyurethanes

Summary – IMPACT™ Technology A Greener ProcessNew Polyether Technology Developed and Commercialized.

– First Significant Change in 50 Years of Production. – Technology Relies on Significant Catalyst Invention.– Commercialization Realized with Significant Process Invention.

IMPACT™ Technology is a Greener Technology. – Dramatic Reduction in Energy Use and CO2 Generation.– Complete Reduction in Solid Waste.– Significant Reduction in Aqueous Waste.

Development and Expansion of Technology Continuing.– Licensed to all Major Polyether Producers.– Approximately 50% of Bayer’s Polyether Volume has Developed Technology. – Recent Extension to High and Low Molecular Weight Polyether Grades.– Recent Extension to Incorporate the Use of a Renewable Based Starter (NOP).

Over 3 Billion Pounds of Polyether Produced based on IMPACT™ Technology.

Revolutionary Technology that Couples Positive Environmental Effects with Increased Capacity that Optimizes Existing Assets.

Thank You for Your Attention

Polyurethanes

The authors wish to acknowledge the many scientists and engineers that have contributed to the development and commercialization of the IMPACT™ Technology.

Polyurethanes

impact™ technology a greener polyether process -...

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