Progress Report
Li Wei2013.10.11
3 2 2 4 3 2 4 22 ( ) 2 ( ) ( ) 2 ( ) ( ) 2 ( )CH OH l NaNO s H SO l CH ONO g Na SO s H O l
3 3 22 ( ) 2CO CH ONO CO OCH NO
3 3 2
3 3
3
2 2
4 2 4
2 2 2
CH ONO CH OH DMM NO H O
CH ONO MF CH OH NO
CO CH ONO DMO NO
Synthesis of DMC
MN synthesis:
DMC synthesis:
side reactions:
MN
DMC
PdCl2-CuCl2/AC preparation
0.05g PdCl2 and ?g CuCl2
24~25ml 5mol/L HCl
Heat-dissolving
3g AC
Rotary Steaming at 85℃Dry at 120℃ for 4 hThen calcination at 200℃ for 4h
PdCl2-CuCl2 /ACPd:1wt%
Cu:Pd=?:1 (mole ratio)
Immerse
85℃ 4hExcessive impregnation
Cu/Pd (mole ratio)1:1 、 1.2:1 、 1.6:1 、 2:1 、etc
GHSV=8000 h-1 T=110 ℃ , P=0.1MPa(Gauge
pressure)
CO/MN=1:6 ( MN=20% ), N2 ( HCl )
Experiment
1 2 3 4 5 6 7 8 9 10 11 12 13200
250
300
350
400
450
500
550
600
650
Cu:Pd=2:1 Cu:Pd=1.6:1 Cu:Pd=1.2:1 Cu:Pd=1:1
ST
Y (
DM
C)
Time (h)
1 2 3 4 5 6 7 8 9 10 11 12 1340
45
50
55
60
65
70
75
80
85
90
95
100
Cu:Pd=2:1 Cu:Pd=1.6:1 Cu:Pd=1.2:1 Cu:Pd=1:1S
el (
DM
C/M
N)
Time (h)
GHSV=8000 h-1 T=110 ℃ , P=0.1MPa(Gauge
pressure)
CO/MN=1:6 ( MN=20% ), N2 ( HCl )
Experiment
1 2 3 4 5 6 7 8 9 10 11 12 1340
50
60
70
80
90
100
Cu:Pd=2:1 Cu:Pd=1.6:1 Cu:Pd=1.2:1 Cu:Pd=1:1S
el (
DM
C/C
O)
Time (h)
1 2 3 4 5 6 7 8 9 10 11 12 130
10
20
30
40
50
60
Cu:Pd=2:1 Cu:Pd=1.6:1 Cu:Pd=1.2:1 Cu:Pd=1:1
Xco
(%
)
Time (h)
GHSV=8000 h-1 T=110 ℃ , P=0.1MPa(Gauge
pressure)
CO/MN=1:6 ( MN=20% ), N2 ( HCl )
1 2 3 4 5 6 7 8 9 10 11 12 130
10
20
30
40
250
300
350
400
450
500
550
DMM MF DMC DMO
ST
Y
Time (h)
Cu:Pd=1.2:1
1 2 3 4 5 6 7 8 9 10 11 12 130
10
20
30
40
50
60
70
80
90
100
DMC DMO
Sel
/CO
(%
)
Time (h)1 2 3 4 5 6 7 8 9 10 11 12 13
0
10
20
30
40
50
60
Xco
(%
)
Time (h)
1 2 3 4 5 6 7 8 9 10 11 12 130
5
80
85
90
95
100
DMM MF DMC DMO
Sel
/MN
(%
)
Time (h)
Cu:Pd=1.2:1
GHSV=4000 h-1 T=110 ℃ , P=0.1MPa(Gauge
pressure)
CO/MN=1:6 ( MN=20% ), N2 ( HCl )
1 2 3 4 5 6 7 8 9 10 110
5
10
15
70
75
80
85
90
95
100
DMM MF DMC DMO
Sel
/MN
(%
)
Time (h)
1 2 3 4 5 6 7 8 9 10 110
10
20
30
40
50
60
70
80
90
100
DMC DMO
Sel
/CO
(%
)
Time (h)
1 2 3 4 5 6 7 8 9 10 110
10
20
30
40
50
60
70
80
Xco
(%
)
Time (h)
1 2 3 4 5 6 7 8 9 10 110
10
20
200
250
300
350
400
DMM MF DMC DMO
ST
Y
Time (h)
Cu:Pd=1.2:1
GHSV=3000 h-1 T=110 ℃ , P=0.1MPa(Gauge
pressure)
CO/MN=1:6 ( MN=20% ), N2 ( HCl )
1 2 3 4 5 6 7 8 9 10 110
10
20
30
40
50
60
70
80
Xco
(%
)
Time (h)
1 2 3 4 5 6 7 8 9 10 110
10
20
30
40
50
60
70
80
90
100
DMC DMO
Sel
/CO
(%
)
Time (h)
1 2 3 4 5 6 7 8 9 10 110
5
10
15
70
75
80
85
90
95
100
DMM MF DMC DMO
Sel
/MN
(%
)
Time (h)
1 2 3 4 5 6 7 8 9 10 110
5
10
15
150
200
250
300
DMM MF DMC DMO
ST
Y
Time (h)
1 2 3 4 5 6 7 8 9 10 11100
150
200
250
300
350
400
450
500
CO:MN=1:6 CO:MN=1:4 CO:MN=1:2
ST
Y o
f D
MC
(g(
L-c
at)-1
h-1
)
Time (h)1 2 3 4 5 6 7 8 9 10 11
0
20
40
60
80
100
CO:MN=1:6 CO:MN=1:4 CO:MN=1:2
ST
Y o
f D
MO
(g(
L-c
at)-1
h-1
)
Time (h)
Cu:Pd=1.2:1 CO:MN=1:6/1:4/1:2
GHSV=4000 h-1 T=110 ℃ , P=0.1MPa(Gauge
pressure)
CO/MN=1:6/1:4/1:2 ( MN=20% ), N2 ( HCl )
1 2 3 4 5 6 7 8 9 10 1150
55
60
65
70
75
80
85
90
95
100
CO:MN=1:6 CO:MN=1:4 CO:MN=1:2
Sel
DM
C/M
N (
%)
Time (h)
1 2 3 4 5 6 7 8 9 10 1150
60
70
80
90
100
CO:MN=1:6 CO:MN=1:4 CO:MN=1:2S
el D
MC
/CO
(%
)
Time (h)
1 2 3 4 5 6 7 8 9 10 110
5
10
15
20
25
30
35
40
CO:MN=1:6 CO:MN=1:4 CO:MN=1:2
Sel D
MO
/CO
(%
)
Time (h)
1 2 3 4 5 6 7 8 9 10 110
5
10
15
20
CO:MN=1:6 CO:MN=1:4 CO:MN=1:2
Sel D
MO
/MN
(%
)
Time (h)
GHSV=4000 h-1 T=110 ℃ , P=0.1MPa(Gauge
pressure)
CO/MN=1:6/1:4/1:2 ( MN=20% ), N2 ( HCl )
Cu:Pd=1.2:1 CO:MN=1:6/1:4/1:2
Cu:Pd=1.2:1 CO:MN=1:6/1:4/1:2
GHSV=4000 h-1 T=110 ℃ , P=0.1MPa(Gauge
pressure)
CO/MN=1:6/1:4/1:2 ( MN=20% ), N2 ( HCl )
1 2 3 4 5 6 7 8 9 10 110
10
20
30
40
50
60
70
80
90
100
CO:MN=1:6 CO:MN=1:4 CO:MN=1:2
X
co (
%)
Time (h)
Work plan
1. Optimization of process conditions
1.1 CO/MN ( Volume ratio ): 1:6 、 1:4 、 1:2 ( MN=20% )GHSV=3000 h-1 , T=110 ℃ , P=0.1MPa(Gauge pressure) , N2 ( HCl )
1.2 T (℃): 100 、 110 、 120
GHSV=3000 h-1 , P=0.1MPa(Gauge pressure) , CO/MN=1:6 ( MN=20% ), N2 ( HCl )
1.3 P ( MPa , Gauge pressure ): 0.1 、 0.2 、 0.3
GHSV=3000 h-1 , T=110 ℃ , CO/MN=1:6 ( MN=20% ), N2 ( HCl )
Work plan
2. Preparation of Catalyst
2.1 Loading of active components
1.Solvent H2O 、 HCl 、 NH3▪H2O 、 CH3OH
2. Loading of active components Incipient impregnation 、 Excessive impregnation
Work plan
2.2 AC pretreatment
2.2.1 Chemical treatments ⑴ Redox modification ① HNO3 、 H2O2
② H2
⑵ Acid and alkali treatments ① HCl ② NaOH 、 KOH ③ NaOH+HCl 、 KOH+HCl2.2.2 Thermal treatments ① N2 : 600℃ 、 700℃ 、 900℃ ② H2 : 600℃ 、 700℃ 、 900℃
Thank you
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