The Influence of the binder on

the Product and Application

Related Properties of Zeolite

Molecular Sieves

Dr. Kristin Gleichmann

and

Dr.-Ing. Jens Zimmermann

Leipzig, 14 May 2019

• Introduction

• Manufacturing of zeolite molecular sieves

– Binder containing zeolite granulates

– Binderfree zeolite granulates

• Lab-scale tests for determination zeolite properties

– Behavior under applied stress

– Breakthrough properties

• Summary

Outline

2

Introduction

3

SeparationsReactors

J. Pendergast, DOW Chemicals

Separation techniques: Distillation, Drying, Extraction, Adsorption…

Separation substances are a main task in many industries

During production attention must be paid to defined product characteristics

LHC-8 Freeport, TX

4

Drying /

Calcination (Activation)Packaging

Drums, Big Bags

Quality Control,

Storage,

Shipping

Shaping

Raw Materials(Water Glass,

Sodium Aluminate,

Sodium Hydroxide, ...)

Filtration Filtration/

Drying

Gel Precip-

itationModification(Ion Exchange,

Dealumination)

Crystallization(Atmospherically,

Autoclave)

Binder MaterialManufacturing Process

o agglomeration

granulation

o spray granulation or

o extrusion

• Mineral binders and/or synthetic binders

• Binder material type and amount influences

- bulk density

- strength

- attrition

- adsorption kinetics

- behavior under harsh conditions (temperature/

concentration shocks)

Binder Material

5

Synthetic Binder Material

- Silica

- Water glass

- …

Mineral Binder Material, e.g.

Binder Material

6

[1] B. Ullrich, M. Dietze, F. Haubrich, Journal of Central European Geology, 56/2, 2010, 115-125

[1]

Attapulgite BentoniteSepiolite Kaolinite

7

Binder Containing Zeolite Beads

- Binder containing zeolite NaMSX

(zeolite 13X = Si/Al = 1.25 /

zeolite NaMSX = Si/Al ~ 1.17)

- Attapulgite bonded

binder ‚net‘

Zeolite crystals

- Mechanical stability through embedding

of zeolite crystals into the binder net

8

Binder

Conversion

Drying /

Calcination (Activation)Packaging

Drums, Big Bags

Quality Control,

Storage,

Shipping

Shaping

Raw Materials(Water Glass,

Sodium Aluminate,

Sodium Hydroxide, ...)

Filtration Filtration/

Drying

Gel Precip-

itationModification(Ion Exchange,

Dealumination)

Crystallization(Atmospherically,

Autoclave)

Mineral

Binder /

Synthetic

Binder /

additives

Manufacturing Process

Binderfree Zeolite Beads

9

- Binder-free zeolite NaMSX

- Mechanical stability through intergrowth

of zeolite particles

- Adsorption capacity higher than for binder

containing zeolites (similar to pure zeolite

powder)

- Faster kinetics through better access to the

interior of the bead

- BUT: Due to the higher capacity and

faster adsorption kinetics larger adsorption

heat amount leads to destruction of bead

shape (only in case of liquid water)

Lab-scale tests for determination

of zeolite properties

10

main tasks of an adsorbent:

- selectivity

- high capacity

- good kinetics

- process stability

Lab-scale tests for determination

of zeolite properties

11

process stability:

- thermal stress,

- spill or carry over resistance,

- binder leaching resistance

Lab-scale tests for determination

of zeolite properties

12

Behavior under applied stress:

- Cyclic-Burst-Unit

- Adsorption-Desorption-Test-Device

- Breakthrough-Unit

Lab-scale tests for determination

of zeolite properties

13

Cyclic-Burst-Unit:

- a full cycle contains two steps:

- Heating out the material at 300 °C,

- Drop the activated and still hot material into water

- Only applicable for binder containing granules

Lab-scale tests for determination

of zeolite properties

15

Adsorption-Desorption-Test-Device

Lab-scale tests for determination

of zeolite properties

16

Breakthrough properties

Test-Conditions:

- Temperature: RT

- Pressure: 5 bar a,

- Superficial velocity: approx. 0,09 m/s

- CO2-Concentration: 445 ppm

- Constant bulk height of 96 cm

QIRC

PIRC

TIC

TIC

TIC

TIC

MFC

MFC

MFC

HT

X

Ad

so

rbe

r

Lab-scale tests for determination

of zeolite properties

17

0

5

10

15

20

25

30

35

standard Binder-system 1 Binder-system 2 Binder-system 3

Cru

sh

Str

en

gth

[N

]

Type

Cyclic-Burst-Test

original

2. cycle

4. cycle

6. cycle

8. cycle

10. cycle

0

5

10

15

20

25

30

35

standard Binder-system 1 Binder-system 2 Binder-system 3

Cru

sh

Str

en

gth

[N

]

Type

Adsorption-Desorption-Test

before

after

Lab-scale tests for determination

of zeolite properties

18

Lab-scale tests for determination

of zeolite properties

19

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

850 950 1050 1150

rela

tive

Co

nc

en

tra

tio

n[c

/c0]

Time [min]

CO2 - Breakthroughcurves on different CWK-Materials

standard #1

standard #2

standard #3

BF-system #1

BF-system #2

BF-system #3

Binder containing Binder free

Lab-scale tests for determination

of zeolite properties

20

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

850 950 1050 1150

rela

tive

Co

nc

en

tra

tio

n[c

/c0]

Time [min]

CO2 - Breakthroughcurves on different CWK-Materials

standard #1

standard #2

standard #3

BF-system #1

BF-system #2

BF-system #3

Binder-system 1 #1

Binder-system 1 #2

Binder-system 1 #3

Binder containing Binder-system 1 Binder free

Lab-scale tests for determination

of zeolite properties

21

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

850 950 1050 1150

rela

tive

Co

nc

en

tra

tio

n[c

/c0]

Time [min]

CO2 - Breakthroughcurves on different CWK-Materials

standard #1

standard #2

standard #3

BF-system #1

BF-system #2

BF-system #3

Binder-system 1 #1

Binder-system 1 #2

Binder-system 1 #3

Binder-system 2 #2

Binder-system 2 #3

Binder-system 2 #4

Lab-scale tests for determination

of zeolite properties

22

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

850 950 1050 1150

rela

tive

Co

nc

en

tra

tio

n[c

/c0]

Time [min]

CO2 - Breakthroughcurves on different CWK-Materials

standard #1

standard #2

standard #3

BF-system #1

BF-system #2

BF-system #3

Binder-system 1 #1

Binder-system 1 #2

Binder-system 1 #3

Binder-system 2 #2

Binder-system 2 #3

Binder-system 2 #4

Binder-system 3 #1

Binder-system 3 #4

Binder-system 3 #5

Summary

23

Investigated several new binder-systems

Identified a systems that fits well to the well known standard

material

- mechanical and application stress tests fulfilled

- further investigations in breakthrough behavior needed

25

0,0

0,5

1,0

1,5

2,0

2,5

3,0

3,5

4,0

4,5

standard-system binder-system 1 binder-system 2 binder-system 3 BF-system

sp

ecif

ic C

O2

-Cap

acit

y [

gra

mm

CO

2 p

er

100 g

ram

m M

S]

Type of material

Specific CO2-Capacity of different Binder-Systems at the Beginning and the End of a CO2-Breakthrough

start

end