‫اشکال و نقشه های اختراع‬

‫او ه ‪Zr‬‬ ‫ا‬ ‫
ت‬ ‫او ه ‪Ti‬‬ ‫ا‬ ‫ا
‬

‫‪ZrO(NO3)2.6H2O‬‬ ‫ی ن‬ ‫‪TiCl4‬‬ ‫‪NH4OH‬‬ ‫ل‪%‬‬

‫‪h‬‬ ‫ه‬ ‫ای ‪C‬‬ ‫اخت‬

‫=‪(ZrO2‬‬ ‫و‬ ‫)‪wt.%‬‬

‫نا‬ ‫ل‬ ‫وا و‬ ‫ه‬ ‫
‬ ‫
ت‬

‫ه =‪pH‬‬ ‫ا
‬ ‫ای ‪ºC‬‬

‫ای ‪ºC‬‬ ‫‪h‬‬ ‫ه‬ ‫اخت‬

‫ای ‪C‬‬ ‫‪h‬‬ ‫ر
ا ی ه‬

‫های ر‬ ‫ه‬ ‫ا‬ ‫ی ن‬ ‫و ش تش ا‬ ‫ر‬ ‫ا‬

‫ها‬ ‫‪h‬‬ ‫ه‬ ‫ای ‪ºC‬‬ ‫ر‬ ‫خش‬

‫ها‬ ‫‪h‬‬ ‫ه‬ ‫ای ‪ºC‬‬ ‫ا
‬

‫تا‬
‫ا ه های نان ا ا‬
‫‪ZrO2, TiO2(25)-ZrO2(75), TiO2(50)-ZrO2(50), TiO2(75)-ZrO2(25), TiO2‬‬

‫‪.‬‬ ‫شکل ‪
-‬ت ا ه ‪ TiO2-ZrO2‬نان
اختا ه وش
‬

‫اه‬ ‫او ه ‪Cr‬‬ ‫ا‬ ‫
ت‬

‫‪TiO2-ZrO2‬‬ ‫‪Cr(NO3)3·9H2O‬‬
‫ی ن‬
‫=‪(ZrO2‬‬ ‫و‬ ‫)‪wt%‬‬ ‫)‪(Cr2O3 : wt%‬‬

‫ای ‪ºC‬‬ ‫‪h‬‬ ‫ه‬ ‫ا و ‪rpm‬‬ ‫اخت‬

‫ا و ‪rpm‬‬ ‫ای ‪C‬‬ ‫‪h‬‬ ‫ه‬ ‫ق‬

‫ها‬ ‫‪h‬‬ ‫ه‬ ‫ای ‪ºC‬‬ ‫ر‬ ‫خش‬

‫ها‬ ‫‪h‬‬ ‫ه‬ ‫ای ‪ºC‬‬ ‫ا
‬

‫‪Cr/TiO2-ZrO2‬‬ ‫شکل ه نان ا ا‬

‫‪Cr/ZrO2, Cr/TiO2(25)-ZrO2(75), Cr/TiO2(50)-ZrO2(50), Cr/TiO2(75)-ZrO2(25), Cr/TiO2‬‬

‫ه وش ق ‪.‬‬ ‫‪Cr/TiO2-ZrO2‬‬ ‫های‬ ‫شکل ‪
-‬ت نان ا ا‬

 Cr2O3 (Rhombohedral, 00-006-0504)
TiO2 (Anatase, Tetragonal, 00-001-0562)
ZrO2 (Tetragonal, 01-080-0784)
ZrO2 (Monoclinic, 00-013-0307)

( ) TiO2(75)-ZrO2(25)

( ) Cr/ZrO2
Intensity (a.u.)

( ) Cr/TiO2(25)-ZrO2(75)

( ) Cr/TiO2(50)-ZrO2(50)

( ) Cr/TiO2(75)-ZrO2(25)

( ) Cr/TiO2

10 20 30 40 50 60 70 80 90
2 (degree)
.Cr/TiO2-ZrO2 ‫های
ت ی‬ ‫ نان ا ا‬XRD ‫ نا‬- ‫شکل‬
( ) TiO2(75)-ZrO2(25) ( ) Cr/ZrO2

( ) Cr/TiO2(25)-ZrO2(75) ( ) Cr/TiO2(50)-ZrO2(50)

( ) Cr/TiO2(75)-ZrO2(25) ( ) Cr/TiO2

.Cr/TiO2-ZrO2 ‫های
ت ی‬ ‫ نان ا ا‬FESEM ‫ نا‬- ‫شکل‬

 100 ( ) TiO2(75)-ZrO2(25)
Min: 16.7 nm
Max: 75.6 nm
80 Average = 33.7 nm
65.2 nm
Standard deviation: 11.7
Frequency (%)

60

36.7 100nm
40

20.4 21.8
20 16.3
4.1
0.0 0.0 0.7 0.0 0.0
0
0-10 20-30 40-50 60-70 80-90
Particle size (nm)
100 ( ) Cr/ZrO2
Min: 17.9 nm
Max: 91.3 nm
80 Average = 40.9 nm
Standard deviation: 14.7 78.3 nm
Frequency (%)

60 52.0
100nm
40

20 16.0
10.0 10.0
6.0 4.0
0.0 0.0 0.0 2.0
0
0-10 20-30 40-50 60-70 80-90
Particle size (nm)
100 ( ) Cr/TiO2(25)-ZrO2(75)
Min: 22.9 nm
Max: 96.7 nm
80 Average = 41.7 nm
Standard deviation: 11.4 96.7 nm
Frequency (%)

60 66.0

100nm
40

20 17.0
10.4
0.0 0.0 2.8 0.9 0.0 0.9 1.9
0
0-10 20-30 40-50 60-70 80-90
Particle size (nm)
.Cr/TiO2-ZrO2 ‫های
ت ی‬ ‫ع ان ا ذ ا نان ا ا‬ ‫ نا‬- ‫شکل‬
 100 ( ) Cr/TiO2(50)-ZrO2(50)
Min: 23.9 nm
Max: 57.8 nm
80 Average = 39.1 nm
69.1 nm
Standard deviation: 8.6
Frequency (%)

60.4
60

100nm
40

18.0 16.2
20
5.4
0.0 0.0 0.0 0.0 0.0 0.0
0
0-10 20-30 40-50 60-70 80-90
Particle size (nm)
100 ( ) Cr/TiO2(75)-ZrO2(25)
Min: 17.9 nm
Max: 57.8 nm
80 Average = 37.8 nm
Standard deviation: 9.5 52.2 nm
Frequency (%)

60 55.6

100nm
40

19.0
20 12.7
7.9 4.8
0.0 0.0 0.0 0.0 0.0
0
0-10 20-30 40-50 60-70 80-90
Particle size (nm)
100 ( ) Cr/TiO2
Min: 18.8 nm
Max: 196.5 nm
80 Average = 42.9 nm 130.4 nm
Standard deviation: 29.9
Frequency (%)

60
49.0
100nm
40

20.4
20 16.3
8.2
2.0 1.0 1.0 1.0 1.0
0
10-20 30-40 120-130 140-150 190-200
Particle size (nm)
‫شکل – ا ا ه‬
 Ti-Zr-O Ti Zr

25.0µm 25.0µm 25.0µm

( ) TiO2(75)-ZrO2(25)
Cr=0 O
Element Gel T75Z25
Cr 0.0 0.0
Ti 70.8 60.0
Zr 29.2 40.0

25.0µm 25.0µm
keV

Cr-Zr-O Ti=0 Zr

25.0µm 25.0µm 25.0µm

( ) Cr/ZrO2
Cr O
Element Gel CrT0Z100
Cr 4.6 6.2
Ti 0.0 0.0
Zr 95.4 93.8

25.0µm 25.0µm
keV

Cr-Ti-Zr-O Ti Zr

25.0µm 25.0µm 25.0µm

( ) Cr/TiO2(25)-ZrO2(75)
Cr O
Element Gel CrT25Z75
Cr 4.9 3.9
Ti 20.2 14.0
Zr 74.9 82.1

25.0µm 25.0µm
keV

.Cr/TiO2-ZrO2 ‫های
ت ی‬ ‫ نان ا ا‬EDX ‫ نا‬- ‫شکل‬

 Cr-Ti-Zr-O Ti Zr

25.0µm 25.0µm 25.0µm

( ) Cr/TiO2(50)-ZrO2(50)
Cr O
Element Gel CrT50Z50
Cr 5.1 6.5
Ti 47.5 33.1
Zr 42.5 60.4

25.0µm 25.0µm
keV

Cr-Ti-Zr-O Ti Zr

25.0µm 25.0µm 25.0µm

( ) Cr/TiO2(75)-ZrO2(25)
Cr O
Element Gel CrT75Z25
Cr 5.4 6.1
Ti 67.0 53.7
Zr 27.6 40.2

25.0µm 25.0µm
keV

Cr-Ti-O Ti Zr=0

25.0µm 25.0µm 25.0µm

( ) Cr/TiO2 Cr O
Element Gel CrT100Z0
Cr 5.7 6.4
Ti 94.3 93.6
Zr 0.0 0.0

25.0µm 25.0µm
keV

‫ ا ا ه‬- ‫شکل‬
 200
Support
180 Nanocatalysts
165.5
Specific Surface Area (m2/g)

160 151.4

140
127.9
120 113.5

100

80

60 57.3

40 28.6
20

0
TiO2(75)-ZrO2(25) Cr/ Cr/ Cr/ Cr/ Cr/
ZrO2 TiO2(25)-ZrO2(75) TiO2(50)-ZrO2(50) TiO2(75)-ZrO2(25) TiO2
Support/Nanocatalyst
.Cr/TiO2-ZrO2 ‫های
ت ی‬ ‫خص ص نان ا ا‬ ‫
ط‬ ‫ نا‬- ‫شکل‬
 2370
3450

1400
1470

1240
1700
1635

520
480
600

430
670
770
( ) TiO2(75)-ZrO2(25)
Transmittance (a.u.)

( ) Cr/ZrO2

( ) Cr/TiO2(75)-ZrO2(25)

( ) Cr/TiO2

4000
400 3500
900 3000
1400 2500
1900 2000
2400 1500
2900 1000
3400 500
3900
Wavenumber (cm-1)
.Cr/TiO2-ZrO2 ‫های
ت ی‬ ‫ نان ا ا‬FTIR ‫ نا‬- ‫شکل‬
 PI-04

MFC (04) N2

PRV-04 V-04
Notations:
C: Cylinder PI: Pressure Indicator
PI-03 GC: Gas Chromatography PRV: Pressure Regulator Valve
GCS: Gas Collector System R: Reactor
MFC (03) N2 MFC: Mass Flow Controller TIC: Temp. Indicator & Controller
MFM: Mass Flow Meter 4WV: 4-Way Valve
PRV-03 V-03

GCS-01 N2
PI-02 PI-05
4WV-01
CO2 Feed
MFC (02) MFM (01)
Feed to reactor
PRV-02 V-02
Feed
to analyzer
PI-01
Vent
MFC (01) C2H6
Reactor Reactor
4WV-02 outlet inlet
PRV-01 V-01

N2 N2 CO2 C2H6 Cooler

Ar
Gas mixture
Air Electrical heating
H2 to GC
furnace with
temperature
Vent controller

GC-01 Temperature
Controlled
N2 N2 CO2 C2H6 Controller
power supply
GC
Ar Air H2
TIC-01
R-01
C-01 C-02 C-03 C-04 C-05 C-06 C-07 Furnace/Reactor

.‫ب ل ا ا ش ا ا ه ا ن‬ Cr/TiO2-ZrO2 ‫های
ت ی‬ ‫ع کر نان ا ا‬ ‫
ا انه ا ا‬-9 ‫شکل‬

‫ب لا اش اا ه‬ Cr/TiO2-ZrO2 ‫های
ت ی‬ ‫ع کر نان ا ا‬ ‫ ص ری ا
ا انه ا ا‬- ‫شکل‬

.‫ا ن‬
 50
Blank C2H6/CO2/N2 = 10/50/40
GHSV = 9000 h-1
TiO2(75)-ZrO2(25)
40
C2H6 Conversion (%)

Cr/ZrO2

Cr/TiO2(25)-ZrO2(75)
30
Cr/TiO2(50)-ZrO2(50)

Cr/TiO2(75)-ZrO2(25)
20
Cr/TiO2

10

0
550 600 650 700
Temperature (°C)
.Cr/TiO2-ZrO2 ‫ت ای
ت ی‬ ‫ ب ل ا ا ش ا ا ه ا ن وی نان ا ا‬- ‫شکل‬

50
Blank C2H6/CO2/N2 = 10/50/40
GHSV = 9000 h-1
TiO2(75)-ZrO2(25)
40
Cr/ZrO2
C2H4 Yield (%)

Cr/TiO2(25)-ZrO2(75)
30
Cr/TiO2(50)-ZrO2(50)

Cr/TiO2(75)-ZrO2(25)
20
Cr/TiO2

10

0
550 600 650 700
Temperature (°C)
.Cr/TiO2-ZrO2 ‫های
ت ی‬ ‫ا ن وی نان ا ا‬ ‫ ان ا‬- ‫شکل‬
 C2H6 Conversion (%) C2H4 Yield (%)
120 C2H4 Selectivity (%) Cr/TiO2(75)-ZrO2(25)
C2H6/CO2/N2 = 10/50/40
T = 700ºC GHSV = 9000 h-1
100

80
Percent

60

40

20

0
0 60 120 180 240 300 360 420 480 540 600
Time on stream (min)
.‫ب ل ا ا ش ا ا ه ا ن‬ Cr/TiO2(75)-ZrO2(25) ‫
تی‬ ‫ا ا ی نان ا ا‬ ‫ا‬ ‫ا ا‬- ‫شکل‬