Emission Characteristics of Air Pollutants by Typical Production Process in Iron and Steel Enterprises
Xue Zhigang, Ma jinghua, Li Chongqing, Duan Jingchun
Chinese Research Academy of Environmental Sciences
(CRAES)
May. 12, 2010
Background
Test Plan
Test Results
Conclusion & Suggestions
Content
15155 18155222332829135237
12700124001145910894101249536500 0500 0500 0500 01000 01000 01000 01000 01500 01500 01500 01500 02000 02000 02000 02000 02500 02500 02500 02500 03000 03000 03000 03000 03500 03500 03500 03500 04000 04000 04000 04000 019 95年19 95年19 95年19 95年 19 97年19 97年19 97年19 97年 1 999年1 999年1 999年1 999年 2 001年 2 001年 2 001年 2 001年 20 03年20 03年20 03年20 03年 20 05年20 05年20 05年20 05年产量（万吨）产量（万吨）产量（万吨）产量（万吨）
In 1995, China's steel output was 95 million tons, 352 million tons in 2005 ,
and 500 million tons in 2008, it is estimated that by 2010, China's steel output
will reach 550 million tons; in 2005, the SO2 and dust emissions by China's steel
industry were 4,862,700 tons and 1,550,400 tons respectively, with increases
of 3,546,700 tons and 1,130,800 tons respectively over 1995.
00001001001001002002002002003003003003004004004004005005005005006006006006001995年 1997年 1999年 2001年 2003年 2005年排放量（万吨
）排放量（万吨）排放量（万吨）排放量（万吨） 二氧化硫 烟尘
Pollutant Emission
10,000 tons
Output
10,000 tons
1995 1997 1999 2001 2003 2005
SO2
sulfur dioxide
smoke dust
1995 1997 1999 2001 2003 2005
Background
Typical Production Process Flow
of Iron & Steel Industry
,NOx
Transport &
StorageCrushing
Ore Sintering
Coal Coking
LimeRoasting
Crushing Or
ScreeningIron
Making
HotMetalPre-
treatmentSteel-Making
Steel ColorTreat-ment
CastingOr
Contin-Uous
CastingHeating
HotScarfing
HotRolling
&Cold Rolling
SteelProduct
PM,CO,SO2,NOx
Emission Factors of Air Pollutants by Iron & Steel Industry
2-510-17Kg/t steelDustSteel Making（Electric
Furnace）
0.1-0.535-57Kg/t steelDustSteel Making（Converter）
2-520-30Kg/t steelDustSteel Making
（Open-hearth Furnace）
0.08-0.1140-60Kg/t ironDustIron Making
2-152-15Kg/t sinterSulfur dioxide
0.1-125-60Kg/t sinterDustSinter
0.1-0.61.4-3.0Kg/t cokeSulfureted
hydrogenCoking
Pollutant Emission
Factors
Pollutant Producing
FactorsUnitPollutantProduct
From:Industrial Pollutants Producing and Emission Factors Handbook Compiled by SEPA in 1996.
Dust—Sampling by filter cartridge,
Qingdao Laoyin Model 3012H
Automatic Smoke Dust (Flue gas)
Sampling and Measuring System.
Stage 1 2 3 4 5 6 7 8 9 10 11 12 13
Cutpoint Diameter
(µm)0.028 0.054 0.095 0.157 0.263 0.382 0.613 0.948 1.6 2.39 4 6.68 9.92
Geometric Mean
Diameter (µm)0.04 0.07 0.12 0.2 0.32 0.48 0.76 1.23 1.96 3.09 5.17 8.14
Sampl-ing Gun
PM10Pre-cutter（（（（Whirlwind Dust
Remove））））Sampl
-ingPump
ELPIELPI can measure PM with aerodynamic
diameter from 28nm to 9.9µm，，，，and classify
them into 12 stages for separate counting。。。。
Inhalable PM
—Electrical Low Pressure
Impactor (ELPI) by Dekati
Ltd., Finland
Test Method
Particulate Size Distribution Sampling and Measuring System
Chemical Composition Analysis Method of Particulate Matter
� Elements Analysis: Microwave-assisted digestion+
inductively coupled plasma mass spectrometry (ICP-MS)
� OC/EC Analysis: Sunset Carbon Analyzer (Sunset
Laboratory Inc., USA), thermophotometry.
� Ion Analysis: Dionex-600 Ion Chromatographic
Analyzer
Data Analysis and Processing
� ELPI attached working sheet
NMHCs Sampling
Coke Oven Roof Sampling：：：：� Sampling canister: check the canister before sampling, ensure that there is no
target compound in it, then vacuum it, open the valve till the internal and external air pressure are the same, start sampling, control the air flux by adjusting flow-limiting valve to prolong sampling time, there is a filter (cotton) in front end for filtering fine dust in the air, tighten the valve after sampling.
Flue Gas Sampling
� Before sampling, connect the pump with PTFE pipe to extract smoke air until all the air in the pipe and pump are replaced, immediately connect the pipe with sampling canister for sampling.
NMHCs Analysis
Controlled by quality flow controller to stabilize the extracting flux
Twograde
cold trapfor removing
H2OandCO2
GC/MSD Analysis
Cryogenic FocusingSampling Canister
Prethickening System
Sampling Site
Sintering Plant
——Charge end (head) of sintering machine, Sintering machine tail.——Dust Collector :4 electric fields ESP.
Iron Plant——Blast furnace cast house——Dust Collector :FF.
Flue Gas ESP/FFESP/FFESP/FFESP/FF Induce
Draft FanChimneyESP/FFESP/FFESP/FFESP/FF
Test Plan
Coke Oven's Carbonization
Chamber
Coke Oven's Heating System
Coal Charger
Coal TowerRaw Gas System
Gas Puri-
Fica-
tionsyst
em
Coke
Guide
Coal Charging Coal Charging Coal Charging Coal Charging Dust CollectorDust CollectorDust CollectorDust Collector Coke Pushing Dust Coke Pushing Dust Coke Pushing Dust Coke Pushing Dust CollectorCollectorCollectorCollectorCoke Quenching Car
Coke Quenching TowerCoke Screening SystemCoke
Push-
er
Exhaust Gas by Exhaust Gas by Exhaust Gas by Exhaust Gas by Coal ChargingCoal ChargingCoal ChargingCoal ChargingExhaust Gas by Coke Exhaust Gas by Coke Exhaust Gas by Coke Exhaust Gas by Coke RecoveryRecoveryRecoveryRecovery
Coke TransportRed Coke
Recycled Coal Recycled Coal Recycled Coal Recycled Coal GasGasGasGas
Coke Quenching Coke Quenching Coke Quenching Coke Quenching Dust Dust Dust Dust CollectorCollectorCollectorCollector Exhaust Gas by Coke Exhaust Gas by Coke Exhaust Gas by Coke Exhaust Gas by Coke QuenchingQuenchingQuenchingQuenching
Coal Blending
Blast F
urn
ace
Gas A
ir
Gas
Tran
smissio
n
烟囱
Coking Plant Sampling Site
Sampling Frequency
dittodittoBehind Dust
Removal
Device
ditto
dittodittoIn front of
Dust Removal
Device
FFcast
house
Iron
Plant2200m
3
dittodittoBehind Dust
Removal Deviceditto
dittodittoIn front of
Dust Removal
Device
dittoTail of
Machine
dittodittoBehind Dust
Removal
Deviceditto
3 groups
Aluminium
film/Teflon
film/quartz film
3 times by
Glass fibre cartridge
filter
In front of
Dust
Removal
Device
ESPHead of
MachineSinter
-ing
Plant
360m2
PM10 Diameter-
Graded SamplingDust SamplingLocation
Dust
CollectorSite
� Sampling Equipment Applied
Coke Oven Roof：：：：PM Sampler
Pump, Sampling canister
Sinter machines’ head and tail, iron making, coal loading, coke pushing, coke quenching ,chimney：：：：Qingdao Laoying Automatic Automatic Smoke Dust (Flue gas) Sampling and Measuring System.
ELPI
Meet
Stand-
ard1503
Blast Furnace
& Blast
Furnace cast
house
99.399.5±±±±0.41560.7±±±±25.4Cast
house
Meet
Stand-
ard99.719.93±±±±1.43445.3±±±±147.6
Tail of
Machine
Meet
Stand-
ard
1503Sinter Machine
(head, ,tail)
98.224.8±±±±2.3270.3±±±±27.5Head of
Machine
Limited
Value
(mg/m3)
Level
of
Stand
-ard
Type
of
Furnace
Behind
Dust
Removal
In front of Dust
Removal
Decision
Out-
comes
National Standard
GB 9078-1996
Dust
Removal
Efficien-
cy(%)
Concentration In Front of
/Behind Dust
Removal(mg/m3)
Site
Dust Emission Concentration and Removal
Efficiency at Each Test Site
Test Results
Size Distribution of Inhalable PM Mass Concentration
Machine head, behind dust removal device
Machine head, in frond of dust removal device
Machine tail, behind dust removal device
Machine tail, in frond of dust removal device
99.3993.4893.2099.7198.4198.3098.2296.5696.55Dust Removal
Efficiency%
9.54.834.349.934.293.624.84.774.08Behind Dust
Removal Device
1560.774.0563.803445.3269.02213.52270.3138.47118.20In front of Dust
Removal Device
DustPM10PM2.5DustPM10PM2.5DustPM10PM2.5
PM Mass Concentration at Cast House（（（（mg/m³））））PM Mass Concentration at Machine
Tail（（（（mg/m³））））PM Mass Concentration at Machine Head（（（（mg/m³））））
Removal Efficiency of Different Particulate Size Stages
at Sampling Sites
At all sites under this study, the law of dust removal efficiency appeared
to be: PM2.5<PM10<Total dust，，，，ESP and FF dust collector have higher removal efficiency on course PM in comparison with fine PM.
Chemical Composition Analysis on PM
� Main chemical composition of PM emitted from
sintering machine head:
SO42->K>OC>Cl->Ca>Pb>Si>Fe>Al>Na。。。。
� Main chemical composition of PM emitted from
sintering machine tail:
Fe >Ca> Si> OC> SO42-> Cl-> Al>Na >K> Mg
� Main chemical composition of PM emitted at cast
house:
Si>Fe>OC>SO42->Al>Cl->Ca >K>Na >Mg
PM Production and Emission per Unit of Product
0.0140.1800.0070.4020.0220.451PM
2.5
0.0160.2090.0080.5070.0250.528PM
10
0.0324.4150.0196.4900.0261.031Dust
Emission at
Cast House
Kg/t-Iron
Production at
Cast House
Kg/t-Iron
Emission at
Machine Tail
Kg/t-Sinter
Production at
Machine Tail
Kg/t-Sinter
Emission at
Machine Head
Kg/t-Sinter
Production at
Machine Head
Kg/t-Sinter
Pollutant
Proportion of PM10, PM2.5 in total dust emission at all Sites
45.68%4.09%36.46%6.20%85.00%43.73%PM2.5（（（（%））））
50.84%4.74%43.20%7.81%99.38%51.23%PM10（（（（%））））
Behind Dust
Removal Device,
Cast House
In Front of Dust
Removal Device,
Cast House
Behind Dust
Removal Device,
Machine Tail
In Front of Dust
Removal Device,
Machine Tail
Behind Dust
Removal Device,
Machine Head
In Front of Dust
Removal Device,
Machine Head
Particle
Diameter
Test Results
Air Pollutant Concentration on Coke Oven Roof
4.00.750.420.350.670.401.910.441.05NMHCs
2.221.852.322.351.692.341.763.22CH4
0.00250.00050.00130.00050.00020.00070.00020.0002B[a]P
0.60.330.630.280.230.310.290.23BSO
2.50.701.290.60.440.90.410.55TSP
Standard Grade 2
AverageConcentration
7654321Sample
mg/m3
Air pollutant concentration on coke
oven roof is far below national
standard.
00. 511. 522. 53
TSP BSO BaP CH4 NMHCs
mg/m
3
熄焦烟气浓度周期变化熄焦烟气浓度周期变化熄焦烟气浓度周期变化熄焦烟气浓度周期变化
Pollutant Emission Concentration of Coal-charging, coke Pushing and quenching
0.220.250.650.400.500.741.731.19291.1 3.6 508.2 172.1 NMHCs
0.712.633.943.130.652.513.803.17795.8 3.2 1386.6 467.7 CH4
0.812.443.270.596.17.26.530.151.11.41.27Smoke
Dust
2785.31596123376047.6117.910343724284.51925581CO
42.9103240163.42.52849.742812SO2
SDMini-
mumMaximumAverageSD
Mini-
mum
Maxim
umAverageSD*
Mini-
mumMaximumAverage
Coke QuenchingCoke PushingCoal ChargingProcess
mg/m3
Dust Emission: Coke pushing>coke quenching >coal charging
CH4, NMHCs emission concentration in coal charging is far greater than it in other processes.
0
50
100
150
200
250
300
350
400
1 2 3 4 5 6 7 8 9 10 11时间min
SO
2
浓度（mg/m3
）0
2000
4000
6000
8000
10000
CO
浓度（mg/m3
）SO2 CO
0. 110
1000
装煤 出焦 熄焦 焦炉顶 环境
mg/m3
TSP CH4 NMHCs
CoalCharging
Coke Pushing
Coke Quenching
Coke Oven Roof Ambient Airt
NMHCs Emission Characteristics
The main composition of NMHCs are: ethene,
benzene, ethane, propylene , toluene, dimethylmethane, butylene etc.
0. 010. 11101001000
装煤 出焦 熄焦 炉顶 环境
浓度mg
/m3烷烃 烯烃苯系物 乙炔
Concentration m
gAlkane
Benzene Series
Alkene
Ethyne
CoalCharging
CokePushing
CokeQuenching
Coke OvenRoof Ambient Air
0
2500
5000
7500
10000
装煤 出焦 熄焦 焦炉顶 环境
1, 2, 3-三甲基苯1, 2, 4-三甲基苯邻乙基甲苯1, 3, 5-三甲基苯对乙基甲苯间乙基甲苯丙基苯异丙基苯邻二甲苯间/ 对二甲苯乙苯苯乙烯甲苯苯
0
300
600
900
出焦 熄焦 焦炉顶 环境
Emission Characteristics of Benzene Series
μg/m3
Coke
Quenching
Coke
Oven Roof
Ambient Air
Coal
Charging
Coke
Pushing
Coke
Quenching
Coke
Oven Roof
TMB
TMB
C9H12
TMB
ethyltoluene
C9H12propylbenzene
isopropyl benzene
C9H12 C9H12
o-xylene
m-xylene,p-xylene
ethylbenzene
styrene
toluene
benzene
Coke
Pushing
Ambient Air
Emission Characteristics of Particle Matter by Coking
47.60.11341.40.21667.90.166PM1
63.50.15190.70.47478.20.191PM2.5
0.2380.5220.244PM10
％Coke
Quenching％Coke
Pushing％Coal
Charging
mg/m3
PM emitted by coking are mainly PM2.5 or below.
Conclusion
� Measurements on three emission sites, i.e. sinter machine head, tail and cast
house in iron plant showed that emission concentration of dust meet the national
standard. In all sites, PM2.5 in flue gas (behind dust removal device) have a high
proportion in PM10 i.e. over 80%,it means: the main composition of PM10 by iron
and steel industry’s typical producing process is PM2.5.
�The main chemical composition of PM in the three emission sites are similar,
such as Fe, Si, Ca, K, Al, Na, SO42- , Cl- and high proportion of organic carbon.
�The concentration of air pollutant from coke oven’s roof is far below national
emission standard.The NMHCs found in smoke samples collected in every
process of coking and at coke oven proof are mainly alkane, cyclanes, alkene,
ethyne and benzene series At coal charging site, CH4 and NMHCs emission are
much greater than other test sites; while the composition of pollutant by coke
pushing and on coke oven roof is mainly benzene series; as for coke quenching
process, the main composition are alkane and ethyne.
Conclusion
� Based on the test results, air pollutant emission level by coking process is obtained, it includes SO2, smoke dust, CH4 and NMHCs，，，，which will be very useful to obtain emission factor of coking sector
� In coking process, PM10 emitted mainly consists PM2.5 or below. The PM
emitted by coal charging process mainly consists of OC, Si, SO42-, Ca; The
PMemitted by coke pushing process mainly consists EC, OC, Ca, K, Al; The PM
emitted in coke quenching process mainly consists OC, Ca.
� It is very important to improve the standards on iron and steel industry’s
pollutant emission, for example: set limited value for PM10 and PM2.5
Concentration.
� Application of large capacity coke oven: reduced operation frequency will
result in less leak points and less pollutant emission.Popularization of dry
quenching：：：：by dry quenching, around 80% of sensible heat of red coke
can be recovered, the coke quality will be improved while the air pollutant
can be greatly reduced.
� Strictly Implement the industry policy, wash out backward coking process.
Strengthen pollutant prevention capability, guide coking industry’s
technology upgrade and structure optimization.
Suggestions
