AutoChem II 2920

Yoon, Sung Ki
sky@protechkorea.co.kr
Contents

Introduction

TPD(Temperature Programmed Desorption)

TPR(Temperature Programmed Reduction)

TPO(Temperature Programmed Oxidation)

Pulse Chemisorption: Metal Dispersion

Maintenance and Sample Information Create

Dynamic Chemisorption

• Stainless Steel • 1100 OC Furnace

• Flow Control(MFC) • TCD(Thermal Conductivity Detector)

• Temperature Control • Vapor Source

• Quartz Reactor(Sample Tube) • Gas Blending

 Temperature Programmed Analysis

1. Gas flows into the analyzer.

2. The gas interacts with the sample as the temperature changes.
3. Gas flows past the detector.
4. The detector collects data.
5. The Software plots and calculates results.

Forbid use of Cl, Br, H2S

and > 15%NH3 gas
TCD(Thermal Conductivity Detector) (Appendix C-1)
 TPD
(Temperature Programmed Desorption)
TPD (Temperature Programmed Desorption)

Determine the number and strength of active sites via desorption

NH3 TPD : Acidity, CO2 TPD : Alkalinity

TCD Signal (a.u.) vs. Temperature

TCD Signal (a.u.) - 10 C/min TCD Signal (a.u.) - 5 C/min TCD Signal (a.u.) - 20 C/min
TCD Signal (a.u.) - 2 C/min TCD Signal (a.u.) - 15 C/min TCD Signal (a.u.) - 7 C/min
TCD Signal (a.u.) - 30 C/min TCD Signal (a.u.) - 4 C/min

0.06
TCD Signal (a.u.)

0.04

0.02

0.00

120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500
Temperature (캜 )
 TPR
(Temperature Programmed Reduction)
TPR (Temperature Programmed Reduction)

Determine the number of Reducible species and temperature

at which Reduction occurs.

Pt on Carbon
Ag2O(Silver(l) Oxide) Reduction Temp. -40oC
 TPR (Temperature Programmed Reduction)

Thermocouple
Temp. Good zone

Sample Bad

Sample Good

Quartz Wool

Temperature(oC)

Temp. Bad zone

 TPO
(Temperature Programmed Oxidation)
TPO (Temperature Programmed Oxidation)

Determine the number of Reducible species and temperature

at which Reduction occurs.

Determine the degree of reduction.

Nickel Catalyst
Recycled catalyst
Pulse Chemisorption
 Plus Metal Dispersion,
Chemisorption Active metal surface area

What is Metal dispersion measurement method?

Metal dispersion is measured by

Measuring chemical adsorption amount

of hydrogen or CO on rare metal.
Pulse Chemisorption (H2, CO Stoichiometric Factor(SF))

H2 adsorption CO adsorption

Bridge type
M(s)+1/2H2(g) → MH(s) M(s)+1/2CO(g)→MCO1/2(s)
Stoichiometirc Factor(SF): 2 Stoichiometric Factor(SF): 2

Pt, Pd, Rh, Ru reference catalyst standardization committee

 Pulse Chemisorption (H2, CO Stoichiometric Factor(SF))

CO
Associative Pts + CO → 1Pts
Chemisorption
H
Dissocicative 2Pts + H2 → 2Pts
Chemisorption
O
Surface reactions 4/3 PtsH + O2 → 4/3Pts + 2/3H2O
H
2/3 PtsO + H2 → 2/3Pts + 2/3H2O
 CO Pulse Chemisorption on Pt-Alumina

TCD Signal (a.u.) vs. Time

TCD Signal (a.u.) - Pt Alumina
0.00

-0.00806
-0.05
TCD Signal (a.u.)

-0.10

-0.15

-0.20

-0.04606 -0.04668 -0.04699 -0.04723 -0.04718

-0.25
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
Time (minutes)
H2-O2-H2 Titration on Pt-Alumina

Traditional technique
for Pt & Pd
Result is comparable
to Static adsorption

Metal must form an

easily reducible
surface oxide
CO – Pulse Chemisorption

Drift
Doublet
Copper(Cu) Pulse Chemisorption (Used Cold Trap: Ar)

Cu or Ag catalysts
Maintenance
 Instrument Schematics

Unit1 > Show Instrument Schematics Unit1 < Enable Manual Control

TCD

MFC

Cold Trap Analysis Loop Vapor

Kwik-Cool Furnace
&
CryoCooler
Mechanical Diagram, 1

Sample Thermocouple

Large Loop

Small Loop

Sample Tube 12mm

Sample Tube 6mm

Mechanical Diagram, 2

Cold Trap
(TPR, Pulse Chemisorption Reduction)
Mechanical Diagram, 3

Furnace Temperature Range

☞ Ambient to 1100 oC
☞ -100 to 1100 oC
(with optional CryoCooler)

Furnace Temperature Rate

☞ Up to 50oC per minute
(-70 to 500 oC)
☞ Up to 30oC per minute
(500 to 750 oC)
☞ Up to 10oC per minute
(750 to 1100 oC)

Cooling Gas Inlet Port:

(House gas)
TCD Gas Calibration
Ex.) 10%H2/Ar Gas Calibration

File < Open << Sample Information Unit1 < TCD Calibration << New
 Ex.) TPR TCD Gas Calibration

100% Carrier

10% H2/Ar : Total 1mV

100% Loop
Typical Gas Connection (Appendix C-2)
Loop Calibration
Ex.) 0.5cc Loop Calibration

File < Open << Sample Information User Injection three times and
Instrument Injection three times
Unit1 > Unit Configuration
Syringe (1 cc and 10 cc)

Metal

1 cc

Don’t Touch Glass

10 cc

1.0 cc Syringe : 0.5 ~ 1 cc Loop Calibration

0.5 cc (Injection quantity : 0.4 cc)

1.0 cc (Injection quantity : 0.8 cc)

10. cc Syringe : 5 cc Loop Calibration

5.0 cc (Injection quantity : 4.0 cc)

Loop Components

The position of the

Smaller Loops

The position of the

Large Loop
Gas Defaults
Options > Sample Defaults… >> Insert
MFC Constant Calculate

..
..
Gas Selections
Unit1 > Gas Selections…
Ex.) Analysis Error (Problem of gas selections)

Error
Side Panel Gas Connections

Preparation Gas

Carrier Gas

Loop Gas
Sample Thermocouple Position
Thermocouple Positions

External Internal
Inside Thermocouple position

Outside Thermocouple Position

Sample Information Method
Experimental (TPD, TPR, TPO, Pulse Chemi-sorption)
Experimental (Temperature, Change gas and another)
Experimental (Temperature, Change gas and another)
Sample Analysis
(Start analysis)
 Start Analysis

Unit1 > Start Analysis

분석에 사용될 TCD Gas Calibration data를
불러오는 곳

Ex.) TPD : 15%NH3/He

실험이면 Calibration data를 불어오고
Next를 눌러주면 됨
Edit Sample Peak
 Peak Editor

Reports > Peak Editor..

Insert New peak으로 edit peak을 삽입하고,

Peak의 left 와 Right Edge부분을 선택하고,
각각을 Mark해 주면 자동으로 Area를 계산함
Report
Start Report(분석결과 확인 방법)

Reports > Start Report (Key: F8) 또는 Close Reports (Key: F9)

분석이 끝났거나 또는 분석이 진행되고 있는 파일을 확인함

Save As를 통해서 여러 형식으로

변경하여 저장할 수 있다.
(ex. txt 파일 xls 파일 등)
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