Activity & Stability of [Emim]2ZnBr2Cl2 & [Bu4N]2ZnBr2Cl2 Catalysts due to Weight Ratio of Substrate/Catalyst & Temperature Variations

Activity & Stability of [Emim]2ZnBr2Cl2 & [Bu4N]2ZnBr2Cl2 Catalysts due to Weight Ratio of Substrate/Catalyst & Temperature Variations

Ethylene Carbonate Synthesis by Coupling Reaction of Ethylene Oxide & Carbon Dioxide in the presence of Ionic Liquids Based Catalysts

Presented by:

Jelliarko P.

Green & Sustainable Chemistry Lab

IntroductionIntroduction

O

OO OC OO

T

Cat+

P

Coupling Reaction in ethylene carbonate production

What is coupling reaction of ethylene oxide and carbon dioxide ?

Advantage

- One step reaction.

- No solvent is required except the product itself.

- High molar substrate/catalyst ratio.

- Simple distillation in product separation

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NNCH3

CH3

+

2

ZnBr2Cl2[Emim]2ZnBr2Cl2

[Bu4N]2ZnBr2Cl2

IntroductionIntroduction

Transition metal-Ionic Liquids Catalysts

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N+

CH 3

C H 3

C H 3

CH 3

2

ZnBr2Cl2

ObjectiveObjective

Objective

ObjectiveObjective

Objective

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Objective

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1. Investigating decomposition of ethylene carbonate alone under vacuum and high temperature.

2. Investigating decomposition of ethylene carbonate in the presence of catalyst under vacuum and high temperature.

3. Investigating activity and stability of catalysts in multiple coupling reactions.

ExperimentsExperimentsA

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1. Investigating Decomposition of Ethylene Carbonate Alone

The reactor was charged with an appropriate amount of EC and was fully vacuumed. Then, temperature was increased step by step to specific value (100 – 170 oC)

After cooling, the mixture was weighted and was taken for GC-MS analysis

2. Investigating Decomposition of EC in the Presence of Catalyst

The reactor was charge with an appropriate amount of EC and catalyst and was fully vacuumed. Then, temperature was increased step by step to specific value (100 – 170 oC)

After cooling, the mixture was weighted and was taken for GC-MS analysis

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3. Investigating activity and stability of catalysts in multiple coupling reactions

[Bu4N]2ZnBr2Cl2 catalyst

0.5 gr of catalyst (1.50 %wt) was loaded into 200 mL stainless-steel bomb reactor. 50 gr of EC acted as solvent was also put in. Then, the reactor was charged with 33.6 gr of ethylene oxide. The bomb then was pressurized with CO2 and heated to specific reaction temperature (100 oC), with the addition of CO2 from a reservoir tank to maintain a constant pressure.

After cooling the reactor, the mixture was weighted and was transferred into distillation apparatus for separation process.

The above procedure was repeated 6 times.

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4. Investigating activity and stability of catalysts in multiple coupling reactions

200 mL stainless-steel bomb reactor was charged with an appropriate amount of catalyst and EC acted as solvent. Then, the reactor was charged with ethylene oxide. The bomb was pressurized with CO2 and heated to specific reaction temperature with the addition of CO2 from a reservoir tank to maintain a constant pressure.

After cooling the reactor, the mixture was purged with nitrogen to remove dissolved CO2 and EO. The reactor and its content were weighted and the second reaction was performed.

ExperimentsExperiments

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Experiments Experiments

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DecompositionApparatus

DecompositionApparatus

Go to VacuumC

on

den

ser

TemperatureTransducer

Reactor

ElectricalHeater

PressureTransducer

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CouplingReactionApparatus

CouplingReactionApparatus

ExperimentsExperimentsExperimentsExperimentsExperimentsExperiments

Reactor

EO

Re

ser

vo

ir

CO

2 R

es

ervo

ir

CO2 Tank

N2 Tank

MagneticStirrer

ElectricalHeater

TemperatureTransducer

Preliminary study showed that decomposition occurred at high reaction temperature.

Decomposition of EC into EO and CO2 was observed from pressure increase and weight loss

Decomposition Test of EC

Temperature (oC)

40 60 80 100 120 140 160

P

0

50

100

150

200

250

EC vapor pressure ?(EC) 1 차(EC) 2 차(EC+Cat)

Condition. 100mmHg

EC + Cat[Bu4N]2ZnBr2Cl2

Vaporpressure

Pure EC

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EC Properties:

m.p. 37 – 39 oC

b.p.

243 – 244 oC/740 mmHg

169 oC/100 mmHg

147 oC/50 mmHg

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Result & DiscussionResult & Discussion

1.50 wt% of [Bu4N]ZnBr2Cl2 showed high activity

and stability over six times coupling reactions (100 0C, 500 psig of press. and 1 h reaction time), and separation processes by reduced pressure distillation.

CO2 Consumption

Result & Discussion

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Temp. (oC) Time (h)

1 0.12 10088 150 1 57.80 5833.512 0.12 10088 150 4.33 73.09 1703.813 0.12 10088 150 2 67.02 3382.35

4 0.11 10746 150 1 28.27 3039.785 0.11 10746 150 1 9.82 1055.92

6 0.05 22992 150 1 8.63 19857 0.05 22992 150 1 3.27 753.06

8 0.12 10088 170 1 64.85 6545.429 0.06 20177 170 1 29.64 5983.7

10 0.11 10631 170 1 48.51 5159.5411 0.11 10631 170 1 19.94 2120.79

12 0.05 22728 170 1 10.42 2368.5713 0.05 22728 170 1 5.65 1285.80

TOF (h-1)No. Cat. Wt%Reaction Condition Yield (%)

weightbased

EO/ Cat.MoleRatio

Reaction Condition:

* CO2 Press. 500 Psig.

* EC solvent 39.55 gr

[Emim]2ZnBr2Cl2

Multiple reactions, 1st and 2nd.

All product mixtures were solid white except for 170 oC reaction temperature were slightly yellowish.

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Temp. (oC) Time (h)

1 0.93 1888 100 1 50.00 944.185

2 0.05 34636 130 1 4.46 1546.973 0.05 34636 130 1 0.60 206.26

4 0.11 15929 130 1 9.82 1565.175 0.11 15929 130 1 3.27 521.72

6 0.05 34238 150 1 3.27 1121.417 0.05 34238 150 1 1.19 407.78

8 0.11 16015 150 1 14.58 2324.049 0.11 16015 150 1 3.87 616.58

TOF (h-1) Reaction Condition

No. Cat. Wt%EO/ Cat.

MoleRatio

Yield (%)weightbased

[Bu4N]2ZnBr2Cl2Reaction Condition:

* CO2 Press. 500 Psig.

* EC solvent 39.55 gr

Multiple reactions, 1st and 2nd.

A portion was taken from decomposition test at 150 oC.

All product mixtures were solid white.

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& Discussion& Discussion

[Emim]2ZnBr2Cl2

Wt%Ratio

Activity

ReactionTemp.

Activity

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Result & DiscussionResult & Discussion

[Bu4N]2ZnBr2Cl2Wt%Ratio

Activity

ReactionTemp.

Activity

Result & DiscussionResult & Discussion

“cHRistmAs” CoNcLuSion & Plans“cHRistmAs” CoNcLuSion & PlansA

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Plans

• Finding tune the weight ratio of catalysts over EO that will give the most economical value.

• Recycling coupling reaction test.

Conclusion

• Moderate EC decomposition occurred at high temperature and severe decomposition occurred in the presence of catalysts.

• 1.50 wt% of catalyst ratio showed high durability over multiple coupling reaction and separation processes. ([Bu4N]2ZnBr2Cl2 – study case).

• Above 140 oC, [Emim]2ZnBr2Cl2 showed reduced activity as wt% decreased. However, the activity increased as reaction temperature was raised.

• Above 120 oC, [Bu4N]2ZnBr2Cl2 showed reduced activity as wt% decreased. However, the activity increased as reaction temperature was raised.

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