YNAMISCHE SORPTIONSUNTERSUCHUNGEN AM SYSTEM … · solvent/VOC (depends on T and p) → be sure...

J. Möllmer

DYNAMISCHE SORPTIONSUNTERSUCHUNGEN

AM SYSTEM VOC/AKTIVKOHLE

Institut für Nichtklassische Chemie Leipzig e.V.

Leipziger Symposium 2017

Leipzig, 30.05.2017

Institut für Nichtklassische Chemie e.V.

http://research.uni-leipzig.de/inc/

Outline

• Effects influencing breakthrough curve measurements

→ Dosage of organics

→ Requirements

→ Limitations

• Example I (VOC separation from

biomass plant)

• Example II (VOC/humidity on AC)

Leipzig, 30.05.2017

VOC – Volatile Organic Compounds

Contamination leads to massive health issues like

Cancer, Liver and kidney damage

Central nervous system damage

Vaporizable, carbon-containing compounds

Leipzig, 30.05.2017

Overview – examples for VOC separation

Sorption with activated carbon

Thermal or catalytic

decomposition

→ Breakthrough Testing

Leipzig, 30.05.2017

Overview – Principle of Breakthrough Measurement

Dosage system

Thermostated unit

Reactor/Adsorber

Detector

Mass flow controller bubbler

Glass or metal

version

FID, MS, IR, electrochemical,

others

Off-gas treatment (optional)

Leipzig, 30.05.2017

Dosage system – Example I

Providing a saturated inert gas flow by

- Bubbling with inert gas through one bubbler

Pro Contra

- No heater needed - Only for pure organics

- Easy handling - c0 depends on fill level

adsorber

decrease in c0

no constant dwell time

Leipzig, 30.05.2017

Dosage system – Example II

- Bubbling with inert gas through two bubbler

Pro Contra

- No heater needed - Only for pure organics

- Nearly constant c0 - More complex handling

adsorber

constant c0

nearly

constant dwell time

Leipzig, 30.05.2017

Dosage system – Example III

- Heater/vaporizer – direct injection

Pro Contra

- Miscible liquid mixtures possible - Heater is needed

- Direct control of c0 - Complex equipment

Leipzig, 30.05.2017

Dosage system – limitations

→ Larger concentration is limited due to the csat of the used

solvent/VOC (depends on T and p)

→ be sure that no condensation can occur (heating up tubes)

→ Low concentration is limited due to the csat of the used

solvent/VOC (dilution; lower T possible)

→ normally dilution down to 1:500 works (dilution depends

also on overall flow)

→ Dilution below 1:500 – use premixed testing gases !!!

Leipzig, 30.05.2017

Reactor/Adsorber

Reactor differs in size and geometry

→ dbed : dParticle > 10:1

→ hbed : dbed > 3:1

To do:

- Check bed parameters depending on particle size

- Check bed length and velocity for pressure drop

H.W. Kajszika, Adsorptive Abluftreinigung und Lösemittelrückgewinnung durch Inertgasregenerierung, Utz Verlag, 1998.

dbed = 40 mm

Early breakthrough on wall

→ curve flattens

Minimization of

Bypass flow

Leipzig, 30.05.2017

Reactor/Adsorber

Reactor differs in size and geometry

→ dbed : dParticle > 10:1

→ hbed : dbed > 3:1

To do:

- Check bed parameters depending on particle size

- Check bed length and velocity for pressure drop

H.W. Kajszika, Adsorptive Abluftreinigung und Lösemittelrückgewinnung durch Inertgasregenerierung, Utz Verlag, 1998.

dbed = 40 mm

Early breakthrough on wall

→ curve flattens

Minimization of

Bypass flow Shift

Leipzig, 30.05.2017

Detector

Depends on analytical question

• Number of compounds

• Concentration range (detection limit depends on scope,

but should be at least 100-1000 times lower as c0)

• Check time resolution for online GC systems or ECD

• Coupled systems possible → be sure if the overall flow is

large enough for all analytical devices (e.g. aspirated

IR or µGC)

Leipzig, 30.05.2017

Dead time correction

• Dead time or volume – time is needed for flowing the bed up

to the detection unit

fast process

• Avoid interaction between VOC and tubes/fitting/sealing

• Avoid back mixing in the whole system

Input function –

ideal flow tube

non-PTFE type tube

as transfer-line to FID

Leipzig, 30.05.2017

Summary I

→ Breakthrough measurements can be a complex scenario

→ Modular concept ensure high flexibility

→ Check process conditions and select equipment, but

Down-scaling your process, be careful

Leipzig, 30.05.2017

Example I - Biomass gasification

• Gasification of lignocellulosic biomass, mostly:

• Biomass → Gasification → Purification → Turbine/

Power plant

• Gasification agents: Air, O2, Steam, (CO2)

• Product gas contains: H2 35-45%, CO2 20-25%,

CO 19-25%, CH4 9-11%, CxH2x+y 3-4%, impurities

like benzene, toluene, styrene, …

wood chips

cereal or maize straw

Leipzig, 30.05.2017

Adsorptive Purification – Lab test

Characterization of activated carbon

Isotherms Breaktrough experiments

Static method Dynamic experiment (fixed bed)

Hexane

Cyclohexane

Benzene

Toluene

reactor pump

Leipzig, 30.05.2017

Experimental section: Breakthrough Curves

DynaSorb BT:

→ Dynamic method

→ Fully automated

→ Different adsorber sizes available

→ Temperature measurement inside the

adsorber bed

→ Data collecting and data evaluation

tools (with simulation according LDF-

approach)

DynaSorb BT

Leipzig, 30.05.2017

Adsorptive Purification – Lab test: isotherms

toluene benzene cyclohexane

hexane

relevant concentration range

• Affinity: toluene > benzene >

cyclohexane > hexane

Leipzig, 30.05.2017

Adsorptive Purification – Lab test: breakthrough curves

• Breakthrough of pure vapors benzene and toluene at 35 °C

Variation of c Variation of velocity

• Lower concentration leads to larger breakthrough time

• Higher velocity leads to decrease in breakthrough time

Leipzig, 30.05.2017

• Determination of kLDF from breakthrough experiments at 35 °C

components

(constant

velocity)

toluene benzene cyclohexane hexane

~ 1000 ppm

kLDF / 10-4 s-1 1.75 1.73 1.94 4.33

~ 4500 ppm

kLDF / 10-4 s-1 4.60 4.21 4.27 8.64

~ 9000 ppm

kLDF / 10-4 s-1 6.88 7.57 6.72 10.67

Lorimier et

al. 2005 3.2 – 5.8

C. Lorimier, A. Subrenat, L. LeCoq, P. Le Chloirec, Environ. Technol. 26 (2005), 1217-1230.

• kLDF depends on molecular size:

hexane > benzene > toluene/cyclohexane

Leipzig, 30.05.2017

• Breakthrough of mixed vapors benzene/toluene at 35 °C

• Benzene is displaced by toluene

• Slope of toluene breakthrough flattens

Leipzig, 30.05.2017

• Breakthrough of mixed vapors benzene/hexane at 35 °C

• Benzene is displaced by hexane at low hexane concentration

• Traceable concentration effects

Leipzig, 30.05.2017

Example II – Effect of humidity to sorption of VOC

Important case of application: Effects of humidity

• Waste air/exhaust air cleaning

→ Humidity depends on

conditions at location

http://www.silica.berlin/de/

Leipzig, 30.05.2017

Example II – VOC vs. H2O sorption on AC

• Completely different sorption behaviour due to difference

in physico-chemical properties

IUPAC Technical Report, Pure Appl. Chem. 2015; 87(9-10), 1051-1069

Leipzig, 30.05.2017

Breakthrough curve – H2O

H2O breakthrough at different concentrations

→ H2O breakthrough below inflection point of isotherm shows

typical shape, at higher concentration a stepwise curve is

observed due to capillary condensation

Leipzig, 30.05.2017

Breakthrough curve – H2O

Below 45% RH Above 45% RH

Leipzig, 30.05.2017

Breakthrough curve – H2O (low affinity towards AC?)

→ Strong heat detection during first adsorption due to large

interaction of H2O with ash content of carbon

→ Second heat peak is provided by heat of vaporization

Type V isotherm is coupled with a low affinity?

Leipzig, 30.05.2017

Breakthrough curve – Benzene

Benzene capacity is influenced by humidity

→ Benzene breakthrough flattens for low H2O concentrations

→ Benzene capacity decreases with increasing H2O content

Capacity decreases

Leipzig, 30.05.2017

Breakthrough curve – effect of pre-wetting

Benzene capacity is influenced by pre-wetting of the AC in

dynamic (breakthrough) experiment

→ Capacity of benzene decreases after pre-wetting the AC

→ Long equilibration time for H2O sorption (due to capillary

condensation) leads to an unachievable equilibrium case

Capacity decreases

Kinetics play a major role

Leipzig, 30.05.2017

Summary II

• Breakthrough test ideal for Process Down-Scaling

→ Check general experimental conditions

• Studying sorption under real conditions

→ Kinetics

→ Thermodynamics

→ Detection of heat effects

→ Competitive sorption (complex mixtures possible)

Leipzig, 30.05.2017

Acknowledgement

INC Team

Many thanks for your attention!

http://research.uni-leipzig.de/inc http://www.dynamicsorption.com/

Leipzig, 30.05.2017

References

https://www.helsa.com/helsa-functional-coating/helsa-sorbexx/produkte/helsasorbexx-gs/

http://www.adfis.de/index.php/aktivkohle-fur-aktivkohlefilter/

http://www.dge-wittenberg.de/

http://www.silica.berlin/de/

https://www.slideshare.net/SaifulIslam156/adsorption-process-for-voc-volatile-organic-compounds-copy

https://www.vdi.de/technik/artikel/abgasreinigung-verfahren-der-katalytischen-abgasreinigung-grundlagen-3/

http://www.autobild.de/artikel/katalysator-aufbau-funktion-und-schaeden-8533435.html

http://ecolink.com/voc-compliance-strategies/

http://www.directindustry.com/prod/brooks-instrument/product-14565-432127.html

https://www.pinterest.de/pin/382102349612248994/

http://www.agilent.com/home/more-countries?currPageURL=http://www.agilent.com/en-us/products/gas-

chromatography/gc-systems/490-micro-gc

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