HCN NH3

*
200237

1200 2.78.011.917.122.9/s (600~1200)

HCN NH3 HCN NH3
HCN HCN
NH3 NH3 HCN
HCN NH3
>>>>
NH3 HCN
HCNNH3

TQ54

Formation of HCN and NH 3 during the Rapid Pyrolysis of Coal and Model Compounds
LI Jun,YUAN Shuai, LIANG Qin-feng, ZHOU Zhi-jie*, WANG Fu-chen
(Key Laboratory of Coal Gasification of Ministry of EducationEast China University of Science and
Technology, Shanghai 200237, China)
Abstract: The formation rules and the influencing factors of HCN and NH 3 during the pyrolysis of lignite,
bituminous, anthracite, pyrrole and pyridine at different heating rates and different temperatures in a high
frequency furnace were investigated. Average heating rate was 2.78.011.917.122.9/s at the target
temperature of 1200 during the pyrolysis of different coals, reaction temperature was 600~1200
during the pyrolysis of different coals and model compounds of pyrrole and pyridine . The results indicate
that the yields of HCN during pyrolysis lignite and bituminous decrease with an increasing heating rate,
while HCN yield of anthracite increases and then to be constant with an increasing heating rate. NH3
yields of lignite and bituminous increase, while NH3 yield of anthracite decrease with an increasing
heating rate. HCN yields of lignite and bituminous decrease, while HCN yield of anthracite increases with
an increasing temperature. NH3 yields of lignite, bituminous and anthracite increase and then decrease
with an increasing temperature. The sequence of total-N yields during pyrolysis of different coals at
different heating rates is: Lignite> Bituminous> Anthracite. The sequence of total-N yields during
pyrolysis of different coals at different temperatures is: Bituminous> Lignite> Anthracite. NH3 was the
main nitrogen-containing product during the pyrolysis of pyrrole, while HCN was the main
nitrogen-containing product during the pyrolysis of pyridine.
Keywords: coal; pyrrole; pyridine; nitrogen; HCN; NH3

1
NOX
N NH3

: (973 ) (2010CB227000)(08DZ1200200)
(08XD1401306)
(1985-)Tel02164252831E-mail:lijun8559@126.com

(1974-) E-mail: zzj@ecust.edu.cn

 HCN NH3 [1]

N-5N-6N-Q
N-5 [2-4]
HCN NH3
[5-9] [10]HCN
N-5N-6N-Q NH3
HCN NH3 800
HCN NH3[11,12] [6,13,14] [15-17]
HCNMackie [18] 75
HCN NH3

HCN NH3

HCN NH3 HCN NH3

HCN NH3

2
2.1
1 35mm 200mm
(99.999%)

sample
vent
3
8

4
5

Ar

6
7

2
1
Fig. 1. High frequency furnace rapid pyrolysis system
1- Ar cylinder; 2-Gas flow meter;3-High frequency furnace;4-Quartz reactor; 5.-Induction coil; 6-Crucible; 7-Thermocouple; 8-Gas bottle;
9-bubble stone.

HCN NH3
HCN NH3
2.2
(Lignite)(Bituminous)(Anthracite)
1 124~178m
500ml/min 1200
2.78.011.917.122.9/s 600~1200 350A600~1200
17.116.916.716.516.215.9/s 100
600~1200 100
1
Table 1 Proximate and ultimate analyses of coal samples
Proximate analyses wd/%

Ultimate analyses wdaf/%

Coal samples
A

FC

Lignite

6.99

36.74

56.27

73.64

4.97

1.32

3.24

16.83

Bituminous

6.56

31.79

61.65

80.03

3.24

1.17

2.45

13.11

Anthracite

27.25

7.16

65.59

87.05

1.5

1.03

1.94

9.98

2.3 HCN NH3

HCN 20mmol/L NaOH NH3 1.7mmol/L HNO3
CN- NH4+ Metrohm-861
A Supp 1-250 C 4-100
HCN NH3 N
HCN(NH3 ) =

HCN(NH3 )N(mg)
N(mg)

100%

3
3.1
200A250A300A350A400A 1200
2 2.78.011.917.1
22.9/s

Temperature /

1200 400 350 300 250

200

1000
800
600
400
200
0

50 100 150 200 250 300 350 400

Time /s

2
Fig.2 Heating rate at different heating currents

HCN NH3 34 3
4 HCN NH3

1200
HCN
HCN N-5N-6
HCN
NH3
NH3 NH3
HCN NH3

NH3 N-Q HCN N-5N-6

HCN N-Q
NH3 NH3
34 HCN NH3 >>

10
9
8
7
6
5
4
3
2
1
0

L-HCN-N
B-HCN-N
A-HCN-N

12

16

20

Average heating rate/ /s

24

10
9
8
7
6
5
4
3
2
1
0
0

Yield of NH3-N/%

Yield of HCN-N/%

L-NH3-N
B-NH3-N
A-NH3-N

4
8
12 16 20
Average heating rate/ /s

24

3 HCN

4 NH3

Fig.3 Effect of heating rate on HCN yield

Fig.4 Effect of heating rate on NH 3 yield

3.2
HCN NH3 56 56
HCN NH3
N-5 [3]N-5 HCN NH3N-6
800 [11]N-5N-6

5.5
L-HCN-N
5.0
B-HCN-N
4.5
A-HCN-N
4.0
3.5
3.0
2.5
2.0
1.5
1.0 600 700 800 900 1000 1100 1200
Temperature/

Yield of NH3-N/%

Yield of HCN-N/%

HCN NH3
9
8
7
6
5
4
3
2

L-NH3-N
B-NH3-N
A-NH3-N

600 700 800 900 1000 1100 1200

Temperature/

5 HCN

6 NH3

Fig.5 Effect of temperature on HCN yield

Fig.6 Effect of temperature on NH 3 yield

HCN HCN
HCN

[19,20] HCN
HCN HCN

NH3 NH3
N-5 NH3
800NH3 N-5N-6
N-5N-6 NH3

34 56
400s160s96s70s 52s 1min

(14.11%~15.12%)>(5.36%~6.75%)>(2.76%~4.21%)(6.21%~13.67%)>
(3.94%~5.72%)>(3.38%~6.17%)

3.3
HCN NH3 78

7 HCN NH3

NH3 6 7 NH3
NH3 NH3

Pyridine conversion to HCN, NH3/%

Pyrrole conversion to HCN, NH3/%

N-5
0.5
HCN-N
NH3-N

0.4
0.3
0.2
0.1

600 700 800 900 1000 1100 1200

Temperature/

0.4

HCN-N
NH3-N

0.3
0.2
0.1
0.0

600 700 800 900 1000 1100 1200

Temperature/

8 HCN NH3

7 HCN NH3
Fig.7 Effect of temperature on pyrrole conversion to HCN

0.5

Fig.8 Effect of temperature on pyridine conversion to HCN

and NH3

and NH3

8 HCN NH3 HCN

5 8 HCN
HCN

4
(1) HCN NH3
HCN NH3
(2) HCN NH3

(3) >>
>>
(4) NH3 HCN
NH3 N-5HCN N-6

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