Study of adsorption materials in cigarette filter by ... · Gas chromatography-inverse gas...

Study of adsorption materials in cigarette filter by inverse gas chromatography

Shanghai Tobacco Group Co., LTD

Qing Hua Shanghai Tobacco Group Co., LTD

2015-10-8

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2. Development of GC-IGC systems

1. Introduction

3. Application

4. Outlook

Content

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1. Introduction

High cost

Long period

Poor applicability

S E M

B E T

X P S

structure, Composition

Static process

Can we find a New Method? Adsorption material

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1.1 Principle of inverse gas chromatography (IGC)

Gas Chromatography (GC)

Inverse Gas Chromatography (IGC)

method object method object Time

Time

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1.1 Principle of inverse gas chromatography (IGC)

Gas Chromatography (GC)

Inverse Gas Chromatography (IGC)

method object

method object

Time

Time

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Advantage: Low cost

Short period Good applicability

Real adsorption capacity Dynamic process

1.2 Conventional inverse gas chromatography (IGC)

Disadvantage: Single packed column

cannot be used to study mixed probes.

Single detector increase

the human error of retention time 。

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2.1

Existing Problems : Capillary column and packed column are in one column oven, which cause poor separation of mixing probe. The dead time of packed column is big.

Probe Vaporizer

Sample

Recorder

Column Oven

Gas chromatography-inverse gas chromatography (GC-IGC) system with single column oven

2. Development of GC-IGC systems

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Gas chromatography-inverse gas chromatography (GC-IGC) system with double column ovens

Probe Vaporizer

Capillary Column Oven

Recorder

2.2

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Probe Vaporizer

Heated Transferline


Packed Column Oven

Recorder

2.2

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四通接头

Probe Vaporizer

Heated Transferline

Cross piece

Gas sampler


Packed Column Oven

Recorder

2.2

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四通接头

, ,R TCD R FIDt t t∆ = −

Probe Vaporizer

Heated Transferline

Cross piece

Gas sampler


Packed Column Oven

Recorder

2.2

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Dispersive component of surface free energy

Surface acid-base parameters Ka,Kb

DSγ∆

SaH∆

SaG∆Specific component of

free energy of adsorption

Specific component of enthalpy of adsorption

3. Application

Adjusted retention time

Δt=tR-tM

One type of AC as an example, introducing the calculation process.

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3.1 Physical adsorption capacity

1 2

3 4

Adjusted retention time

2

3

( ) 132 ( ) 1

i

oN

i

o

PPV t F PP

−= ∆ ∗ ∗ ∗

−

Net retention volume

a NG RTInV K∆ = − +Molar free energy of adsorption

Dispersive component of surface free energy

2

2 2

2

2( )

4( )CH

D as

CH CH

GNaγ

γ∆∆ =

, ,R TCD R FIDt t t∆ = −

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ΔGas=-RTIn(VNplor/VNref)= RTIn(VNref) - RTIn(VNplor)

Specific component of free energy of adsorption

SaG∆

3.2 Polar interaction

Acetone

TH

F

Ethanol

Acetonitrile

Inte

nsit

y

Acetone

TH

F

Ethanol

Acetonitrile

Methanol

Time (min) Boiling point (oC)

N-pentane

N-hexane

N-heptane

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3.3 Polar interaction

ΔGas=ΔHa

s-TΔSas

ΔGas/T=ΔHa

s/T-ΔSas

Specific component of enthalpy of adsorption

☞

Probe Ethanol Acetonitrile Acetone Tetrahydrofuran

ΔHas

（kJ/mol） -50.56 -27.4 -26.9 -23.7

SaH∆

0.00205 0.00210 0.00215 0.00220 0.00225 0.00230 0.002350.0040.0060.0080.0100.0120.0140.0160.0180.0200.0220.0240.0260.0280.0300.0320.0340.0360.038 乙醇

乙腈丙酮四氢呋喃

∆ Gas /T

(kJ/

mol

/K)

1/T (1/K)

Ethanol Acetonitrile Acetone Tetrahydrafuran

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3.4 Surface acidity or alkalinity

Surface acid-base paraments

-ΔHas =KaDN + KbAN* ☞

-ΔHas/AN* =KaDN/ AN* + Kb

Ka/ Kb=0.40 （Ka/Kb<1: Lewis basic；Ka/Kb>1: Lewis acidic）

Probe Ethanol Acetonitrile Acetone Tetrahydrofuran

AN* 10.3 4.7 2.5 0.5

DN 19 14.1 17 20

Ka,Kb

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AC Car boxen GDX 102 Tenax TA Si l i ca Gel

0

20

40

60

80

100

120

140

160

180

−∆γ S

D (mJ/m

2)

Sampl es

AC Car boxen GDX 102 Tenax TA Si l i ca Gel

0. 5

1. 0

1. 5

2. 0

2. 5

3. 0

3. 5

4. 0

4. 5

Lewi s basi c

Ka/K

b

Sampl es

Lewi s aci di c

3.5 Surface properties of some solid adsorption materials

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3.5 Surface properties of some solid adsorption materials

0 2 4 6 8 10 12

AA

13Z13X

5A

4A3A

5432

Inte

nsity

(a.u

.)

Retention Time (min)

1

WHP /3

1：Methanol；2：Ethanol；3：Acetonitrile；4：Acetone；5：THF

Sample Pore Size (nm)

Adsorbed probe

3A 0.3 /

4A 0.4 1,2,3

5A 0.5 1,2,3

13X 1.0 1,2,3,4,5

13Z 1.0 1,2,3,4,5

AA Porous 1,2,4,5

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4. Outlook

Study the adsorption capacity of common solid adsorption material

Provide a theoretical basis to modify the existing adsorption materials in cigarette filter

A novel evaluation method of adsorption materials in

Cigarette filter

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Thank you for your attention

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Study of adsorption materials in cigarette filter by ... · Gas chromatography-inverse gas...

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