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Institute for Thermal Power Engineering 浙江大学热能所
Clean Coal Energy and Environmentin China
Prof. Prof. KefaKefa CenCenZhejiang UniversityZhejiang University, , ChinaChina
2005.8.222005.8.22
Institute for Thermal Power Engineering 浙江大学热能所
Low Per Capita Energy Reserves能源人均储量偏低
2000年人均能源储量Per capita energy reserves in 2000
55.4%90 t煤炭Coal
4.3%1074 m3天然气Natural Gas
11.1%2.6 t石油Petrol
占世界平均值比例
Ratio to world average value
人均可开采储量Per capita minable reserves
种类 项ItemCategory
Institute for Thermal Power Engineering 浙江大学热能所
Composition Ratio of Installed Capacity发电装机容量构成比例
1.04.27.51.658.627.1900-9502020
41GW3.98%
36GW3.58%
60GW5.96%
623GW61.9%
246GW 24.45%
1006GW2020
0.93.16.92.060.826.3710-7602015
0.72.35.42.563.6/ (72.7)
25.8550-590(666)
2010
0.52.01.93.566.6/ 25.5430(446)
20050.10.70.34.869.324.83192000
新能源Renewable
%
核电
Nuclear
%
气电
Gas
%
油电
Oil
%
煤电
Coal
%
水电
Hydro
%
总装机Total
GW
Coal power needs 400 X 900 MW Super critical units which consume coal---2 billion ton.燃煤发电净增 400 X 900 MW 超临界机组 需消耗20亿吨煤
Institute for Thermal Power Engineering 浙江大学热能所
Gas emission of total world quantity resulted from coal combustion in
China
71 %67 % 87 %
Percentage by coal (%)
13.5 %CO29. 6 %CO10.1 %NOx15.1 %SO2
8~9 %Energy consumption
percent of total world quantitative
Institute for Thermal Power Engineering 浙江大学热能所
Clean Coal Technology
Coal processing
Coal conversion
Advanced power Generation
Flue gas clean technology
Coal w
ashing
Briquette
Coal w
ater slurry
Coal gasification
Coal liquefaction
Supercritical PF technologies
CFB
PFBC
-CC
IGC
C
Flurgas dust
precipitation
FGD
& D
eNO
x
Other
Pollute Contral
technologies
Institute for Thermal Power Engineering 浙江大学热能所
Coal washing and processing
a) Coal WashingThe Combustion , Gasification andPower Generation Technology ofwashing tailing sludge 煤泥燃烧、气化及发电技术
b) Coal water slurry
The State of Art of Clean Coal technology and The Developing Trends
R & D, Application and Development of Clean Coal Technology
Institute for Thermal Power Engineering 浙江大学热能所
Characteristics of coal washing sludgeCharacteristics of coal washing sludge::1.Particle size<0.5mm,Ash>40%,Moisture>25%1.Particle size<0.5mm,Ash>40%,Moisture>25%2.Non2.Non--Newton fluid, heating value:1000Newton fluid, heating value:1000--3000kcal/kg3000kcal/kg
Coal washing sludge Combustion in CFBCoal washing sludge Combustion in CFB洗煤泥流化床结团燃烧原理洗煤泥流化床结团燃烧原理
Key Techniques and innovations采用大粒度高位给料,以利于燃料形成较大凝聚团
使煤水混合物在流化床内结团燃烧,在较高断面热负荷下实现较高燃烧效率
采用异重流化床技术,以防止凝聚团在流化床内沉积,保证稳定运行。
Large particles feeding at the top of furnace
Conglomerate sludge fired in CFB
Novel technique with different-density bed materials in CFB
Institute for Thermal Power Engineering 浙江大学热能所
0.0
20900
4500
75t/h Slime Fired Boiler Structure in Dongdan Power Plant
东滩75t/h洗煤泥循环流化床锅炉简图
• Now 25 power stations has been built
Institute for Thermal Power Engineering 浙江大学热能所
Replace oil by Coal Water Slurry水煤浆代油燃烧技术
2000年 2010年 2020年 dependence on import(%) 31.0
institute of energyof state planning
commission
45~52 59~62
IEA 61 77IEA 54 72
Dependence on the imported oil of China in 2000-2020
Institute for Thermal Power Engineering 浙江大学热能所
180$/ton; 476$/ton (65$/barrel)
– Year 2005:25.2 billion $; 66.6 billion $.– Year 2010:46.9 billion $; 123 billion $.– Year 2015:81 billion $ ; 214 billion $.– Year 2020:131.5 billion $; 345 billion $.
中国石油的供需问题Supply and demand of oil in china
Price of imported oil in
2000
Price of imported oil in
2005
Replacement of oil by CWSStandard quality of CWS:● concentration:65~70%;● viscosity:~1000CP;● grain size:d<50μm● ash content:A<7%;● sulfur content:S<0.5%。
Institute for Thermal Power Engineering 浙江大学热能所
3.52 MW pilot-
scale test facility
in Zhejiang Univerisity
Institute for Thermal Power Engineering 浙江大学热能所
670t/h (200MW)CWS fired
boiler at Nanhaipower plant,
Guangdong,China
Institute for Thermal Power Engineering 浙江大学热能所
汕头电厂220t/h水煤浆锅炉燃烧效率Combustion efficiency of a 200t/h
CWS fired boiler at Shantou power plant, Guangdong,China
3.652.0522.153.27
carbon in fly ash%
99.5892.031.9280499.7391.882.1560399.7491.112.450299.6091.232.4401
Combustion efficiency
%
Thermal efficiency%
Carbon in bottom ash %
Load %run
Institute for Thermal Power Engineering 浙江大学热能所
Pollution emission from a 220t/h CWS fired boiler at
Maoming power plant
20020.2625.6425.6430.67mg/Nm3Par-ticle
650362.4359.4359.4351.7mg/Nm3NOx
2100541.4585.1585.1634.3mg/Nm3SO2
/180.6177180185t/hload
24th,Jun
23rd,Jun
22nd,Jun
state standard
Ave-rage
timeunitterm
ZJU’s CWS combustion technology have been applied to over 70 boilers.
Institute for Thermal Power Engineering 浙江大学热能所
b) CFBC
d) IGCC
Combined clean coal utilization technologies
Clean Coal Power Generation Technology
The State of Art of Clean Coal technology and The Developing Trends
CFB 降低SOX排放SOx emission reduced by CFB
0 1000 2000 3000 4000 5000 6000
Pulverized Coal
World Bank
US Clean Air Act
European
US Clean Air Act
Typical CFB
mg/MJ
SOURCE: The World Bank Environment Guidelines
W/O Scrubber *
Standard *
Amendment 1995 Limit
Community Standard *
Amendment 2000 Limit
(95% Removal) ** Assumption
4wt% Sulfur ContentHHV=14MJ/kg
0 100 200 300 400 500
EuropeanCommunlty
Standard
Pulverized Coal
World BankStandard
CFB withoutNox Control
CFB with NoxControl
mg/MJ
SOURCE: The World Bank Environment Guidelines
CFB 降低NOX排放NOx emission reduced by CFB
Institute for Thermal Power Engineering 浙江大学热能所
b) CFBCClean Coal Power Generation Technology
International:250MWe CFBC- commercial operation 400Mwe CFBC- design
China:Over 1000 6MWe-125MWe CFBC-OperationImported 300MWe CFBC-demonstration
R & D, Application and Development of Clean Coal Technology
Institute for Thermal Power Engineering 浙江大学热能所
d) IGCCClean Coal Power Generation Technology
International:250MWe coal fired IGCC power plant put into
operation
China:IGCC system and key technology research300~400MWe IGCC demonstration project
R & D, Application and Development of Clean Coal Technology
Institute for Thermal Power Engineering 浙江大学热能所
发展多联产技术Multi-product cogeneration technology
气化炉Gasifier
化工产品Chemical products
液体燃料Liquid fuel
供热Heat supply
发电Power generation
合成气(CO+H2)Synthetic gases
固体燃料Solid fuel
→→ →
煤的清洁、综合利用的预期结果Prediction of Coal Clean Utilization
CWS
GasificationGasification((裂解气化裂解气化))
Coal washing(22.5%)
Construction materials
Cement
Extract vanadium
CoalDeSOx40-50% ash
Semi coke Power
generation
heat & refrigeration
electricitygenerationCoal sludge &
Coal rejectsPower generation
coal gas
Sewage & mud co-fired
Municipal wastes &coal co-fired
Biomass & coal co-fired
煤的清洁、综合利用的预期结果Prediction of Coal Clean Utilization
80kg limestone(石灰石)
1ton coal (煤)
Gasification(气化)
Combustion(燃烧)
Ash utilization(灰处理)
235kg cement(水泥)
1600MW Refrigeration(制冷)
6500MW Heat(供热)
1500kWh Electric(电力)
Residue Char(半焦)
80kg Tar(焦油)
300Nm3 Fuel gas(煤气)
试 验 装 置 系 统 流 程 图Experiment diagram
M
M
M
M
放空
(去固定床)
燃
烧
炉气化炉
放空
布袋除尘+引风
鼓风机
煤气引射器
给砂
给砂
给煤
给煤
P
点火油枪
煤气储罐
紧急排气
工业水
煤气泵煤气燃烧器
阻火器
冷却器2洗涤塔1 洗涤塔2
分离器
过滤器
大水槽冰水
循环水泵
P
P
M
P
M
M
P
M
冷却器1
P
P
P
M
M
P
过热器
烟气冷却器 1
O2
P
P
P
PM
P P P
PP
P
M
煤综合利用多联产系统Multi-generation coal utilization system
cement
multi-generation stone coal utilization system
以煤油、电为主的多联产模式multi-product cogeneration for coal oil and electricity
Coal gasification
Synthetic gas
Gas turbine
Membrane separation
Fuel cell
Oil processing
Synthetic oil
ChemicalProcessing
Flue gas
electricity power
oil
chemical
Institute for Thermal Power Engineering 浙江大学热能所
Near Zero Emissions Near Zero Emissions Coal UtilizationCoal Utilization
Near zero emissions coal utilization technology with Near zero emissions coal utilization technology with combined gasification and combustioncombined gasification and combustion
CoalBiomass
Steam
Char¡¢ash¡¢ CaCO
CaO¡¢ash
Limestone
CO
Pressure or atmosphereCFBcombustor
PressureCFBGasifier
User
SOFCpower
Dust removal
Steam turbine
HRSG CondensationCO disposal
Ash drain
Water
Gas turbine
DustRemovalH2
2
3
H2
H2
2
H2
H2OO2
Air
Gas turbine
AirAirHeater
Exit
AirAir separation
Institute for Thermal Power Engineering 浙江大学热能所
CFB GasifierCO2 acceptor gasification process (~25bar)
• Main reactions in gasifier:C+H2O=CO+H2-131.6kJ/molCH4+H2O=CO+3H2-206.3kJ/molCO+H2O=CO2+H2+41.5kJ/mol
CaO+CO2=CaCO3+178.1kJ/molH2S+CaO=CaS+H2O
CoalBiomass
Steam
Char¡¢ash¡¢ CaCO
CaO¡¢ash
Limestone
CO
Pressure or atmosphereCFBcombustor
PressureCFBGasifier
Ash drain
H2
2
3
O2
Institute for Thermal Power Engineering 浙江大学热能所
CFB CombustorCFB CombustorChar combustion CaCO3 calcinationHydrogen combustion
Main reactions in CFB combustor:
CaCO3=CaO+CO2-178.1kJ/mol
C+O2=CO2+393.791kJ/mol
H2+1/2O2=H2O+286kj/mol
CoalBiomass
Steam
Char¡¢ash¡¢ CaCO
CaO¡¢ash
Limestone
CO
Pressure or atmosphereCFBcombustor
PressureCFBGasifier
Ash drain
H2
2
3
O2
H2 from SOFC
Institute for Thermal Power Engineering 浙江大学热能所
Efficiency calculationEfficiency calculation for a samplefor a sample• Power generation:400MW• Coal gasification ratio: 0.7• Operation Pressure: 25bar• Temperature in the gasifier(K) 1205• Hydrogen production rate(kmol/s) 1.42• System efficiency(%)66.52
Proximate analysis/w%, ar
Ultimate analysis/w%, ar Heat value/MJ/k
g, arM V A C H O N S Qdw
2.7 25.17
21.62 63.39
3.88 6.51 0.78
1.13
23.143
Institute for Thermal Power Engineering 浙江大学热能所
1880 1900 1920 1940 1960 1990 2000 2020
60
50
40
30
20
10
0 First Station
PulverizedCoal
Rankine Barrier
Supercritical Boiler
Thermal Efficiency(%) HHV
USCIGCC
PFBC
IGMCFCTC
IGHTA
AGMCFC
Legend:PFBC -Pressured fluidized-bed combustionIGCC -Integrated gasification-combined cycleIGHTA-Integrated gasification-humid-air turbineIGMCFC -Integrated gasification-molten carbonate fuel cellAGMCFC -Advanced gasification-molten carbonate fuel cellUSC -Ultra super criticalTC -Topping cycle
Efficiency ImprovementWith TimeWith Time
Years
FutureGEN1FutureGEN2FutureGEN3
HUSC
Institute for Thermal Power Engineering 浙江大学热能所
Control of Pollutant EmissionControl of Pollutant Emission
污染物排放控制污染物排放控制
Institute for Thermal Power Engineering 浙江大学热能所
ElementMercury
OxidizedMercury
Gaseous Mercury
Particulate Mercury
Mercury Emission and Control during Coal Mercury Emission and Control during Coal CombustionCombustion
Mercury transportation during coal combustionMercury transportation during coal combustion
Institute for Thermal Power Engineering 浙江大学热能所
Mercury Control ApproachMercury Control Approach
ElementMercury
OxidizedMercury
Gaseous Mercury
Particulate Mercury
• Captured in wet FGD scrubbers
adsorbed onto porous solids
• Subsequent collection in a PM control device
Institute for Thermal Power Engineering 浙江大学热能所
Mercury Control Technology in ZhejiangUniversity
Absorbents
Spray
Additives
Control system
Hg CEM
Coal
AirSeparator
Hg0(g),Hg2+
(g),Hg(s)
Mercury Transportation
Hg0(g),Hg2+
(g) →Hg(s)
Hg2+(g) Hg(s)
Institute for Thermal Power Engineering 浙江大学热能所
Hg removal research in a full-scale semi-dry reactor system
flowmeter
Hg tube
mixbox
oil burner
diesel oil
fan
N2
exhaust fan
separator
fan
Hg
Hg sampling
Hg sampling
compressor
water
fan
Institute for Thermal Power Engineering 浙江大学热能所
Hg removal in flue gas before fabric filter with different absorbents
C/Hg ×103
Institute for Thermal Power Engineering 浙江大学热能所
Fluorine ( F ) emission and control Fluorine ( F ) emission and control during coal combustionduring coal combustion
• Fluorides are one of the most hazardous in atmosphere.
• Its toxicity is 10~100 times higher than sulfur dioxide and nitrogen oxide.
• 1ppb~5ppb of fluorine in the atmosphere is probably harmful to some impressionable plants.
Institute for Thermal Power Engineering 浙江大学热能所
Fluorine in Coal Fluorine in Coal Fluorine concentration values for coals analyzed from Fluorine concentration values for coals analyzed from
China (dry basis)China (dry basis)
33794259~1956Gangue
311058193~3313Stone coal
7241151~615Lignite
2830861~1800Anthracite
8117317~696Bituminous coal
Number ofsample
Average value(ppm)
Range(ppm)
Coal rank
Institute for Thermal Power Engineering 浙江大学热能所
Fluorine Emission during Coal Fluorine Emission during Coal CombustionCombustion
★ Fluorine release rapidly with increase of temperature
★ The transfer ratio of fluorine is:
●about 95% for PC boiler
●about 80 ~ 85% for grate-chain boiler
●about 70~80% for FBC500 600 700 800 900
Temperature T(C)
10
30
50
70
90
F Tranfer ratio (%)
Institute for Thermal Power Engineering 浙江大学热能所
Relationship between fluorine emission standard of Relationship between fluorine emission standard of industrial boiler and fluorine concentration in coalindustrial boiler and fluorine concentration in coal
7%31%90%lignite
4%19%42%Bituminous coal
Ratio over standard 超标煤样数量
比例
corresponding fluorine in coal
old boiler
4%14%45%meager coal
15%30%40%anthracite
407~452 ppm
169~187 ppm
101~112 ppm
50 mg/Nm315 mg/Nm39 mg/Nm3
Third classSecond classFirst class
Attention: Fluorine transfer ratio is assumed at 80%
Institute for Thermal Power Engineering 浙江大学热能所
Fluorine Retention Fluorine Retention Compositions of Compositions of sorbentssorbents
1.900.160.070.000.030.060.375.9849.44造纸厂白泥white mud
0.03916.3522.83.4218.530.35钢渣steel residue
0.050.070.280.080.000.193.005.4260.98电石渣carbide slag
0.000.290.20.21.6253.98石灰矿渣limekiln residue
Na2OK2OSO3TiO
2MgOFe2O3Al2O3SiO2CaOsorbent
Institute for Thermal Power Engineering 浙江大学热能所
950 1000 1050 1100 1150 1200Fuel-bed temp. (¡æ)
0
20
40
60
80
100E
ffici
ency
of f
luor
ine
rete
ntio
n (%
)
1# sorbent2# sorbent
Effect of temperature on fluorine retention
Institute for Thermal Power Engineering 浙江大学热能所
Dioxins emission and control during Dioxins emission and control during
MSW and coal coMSW and coal co--fired processfired process
Institute for Thermal Power Engineering 浙江大学热能所
-所谓二噁英是对多氯二苯并二噁英( polychlorinated dibenzo-p-dioxin, 简称PCDD)和多氯二苯并呋喃
(polychlorinated dibenzofuran,简称PCDF)的俗称。
-PCDDs和PCDFs分别由75 个和135个同族体构成
6
98
7
12
34
O
O
6
987
12
34
O
PCDD PCDF
二噁英(Dioxin)
Dioxins emission data from different zones in the world (g I-TEQ/y)
3.7455.6%
MSW incinerationPercentage%
Taiwan
51.40.4%
791564%
12331
1987
2888Total emissionU.S.A
132~4046.7%~10.9%
141~4425.8%~9.5%
151~5304.1%~8.2%
Power plant boilerPercentage%
294~41910%~15%
538~70615%~22%
1102~143422%~29%
MSW incinerationPercentage%
1960~38332434~46593685~6469Total emissionEuropean
60.92.1%
Power plant boilerPercentage%
67.25Total emission
Zone
110038%
MSW incinerationPercentage%
3.3655.0%
Power plant boilerPercentage%
2005年2000年1995年
Institute for Thermal Power Engineering 浙江大学热能所
Pilot Scale Multi-Function MSW Incineration Furnace 10t/d
10吨/天多功能垃圾焚烧中试试验台
Institute for Thermal Power Engineering 浙江大学热能所
800吨/日大规模清洁焚烧垃圾电厂全景
The overall look of the 800 t/d MSW incineration plant
Institute for Thermal Power Engineering 浙江大学热能所
Dioxin Emission from Qiaosi MSW Incineration Plant in Hangzhou
杭州乔司垃圾焚烧厂的二噁英排放测试结果2004-1-12
106%100%负荷Load
1废气控制标准 standardI-TEQ ng/Nm3
0.009, 0.077 0.034烟气(省环境监测中心测试结果 I-TEQ ng/Nm3 )flue gas
0.0025, 0.00820.0068烟气(比利时SGS实验测试结果 I-TEQ ng/Nm3)flue gas
5.6~11.110.1~12.4烟气含氧量% (oxygen)2003-12-232003-12-24测试日期date
78:2284:16燃料比例(垃圾:煤)
fuel (MSW: coal)
3#焚烧炉
Boiler 21#焚烧炉
Boiler 1设备
Institute for Thermal Power Engineering 浙江大学热能所
Dioxins emission from Power Plant Boilers in Chinaassumption
In 2020, total consumption of standard coal will reach 3 billion tons.
= 1500 g I-TEQ/y EU regulation
15000 g I-TEQ/y National regulation
Equals
4.6 billion tons MSW incineration annual at 0.1 ng I-TEQ/Nm3 emission regulation
0.1 ng I-TEQ/Nm3 ( 0.5 ng I-TEQ/kg coal ) EU regulation
1 ng I-TEQ/Nm3 ( 5 ng I-TEQ/kg coal ) National regulation
We suppose
300MW Boiler stack gas emission
0.01352 ng I-TEQ/kg coal
= 40.56 g I-TEQ/y
Institute for Thermal Power Engineering 浙江大学热能所
Removal of MultiRemoval of Multi--pollutants From pollutants From
Flue Gas by OzoneFlue Gas by Ozone
Institute for Thermal Power Engineering 浙江大学热能所
The Removal Mechanism of Several The Removal Mechanism of Several Pollutants From Flue GasPollutants From Flue Gas
32 SOOSO →+
32 HSOOHSO →+
OHSOHOSO +→+ 322
2323 HOSOOHSO +→+
423 SOHOHHSO →+
4223 SOHOHSO →+
2NONOO →+
223 ONOONO +→+
OHNOHONO +→+ 22
222 NHNONOHNO +→++
2322 NHNONOHNO +→++
3 2
Hg O HgOHg O HgO O
+ →+ → + 3 2
2 2 2
Hg NO HgO NOHg H O HgO H O
+ → ++ → +
Can be high
efficiency removed by wet
scrubber
Lifetime of O3• At the
150℃, the decomposition of O3 is about 28% at 10s.
• The decomposition rate is keeping increased when temperature moved up.0 2 4 6 8 10
0.0
0.2
0.4
0.6
0.8
1.0
[O3]/[O3]0
time s
150℃ 200℃ 250℃
Lifetime of the free radical is usually very
short
Institute for Thermal Power Engineering 浙江大学热能所
Reaction time needed by O3/NO reaction • T=150℃
• At this temperature 0.1s is necessary for the conversion of NO.
• SO, the O3’s lifetime is enough for the reaction.
Institute for Thermal Power Engineering 浙江大学热能所
NO removal by O3• T=100℃;• Resident
time is 0.09s;
• NO,NO2,N2O was measured by Rosemount NGA2000 continue emission monitor systems (CEMS) at 5s/scan.
• More than 80% NO can be oxidized
NO oxidized by O3 at 100℃
0.0 0.2 0.4 0.6 0.8 1.0 1.2
0
20
40
60
80
100
NO
oxi
diza
tion
rate
%
O3/NO stoichiometric ratio
NO oxidized rate
Institute for Thermal Power Engineering 浙江大学热能所
O3 and CO
• It found that CO doesn’t react with O3 below 300℃0
100
200
300
400
500
O3/CO=3.5 300℃
O3/CO=3.5 100℃
CO 浓
度 [ppm]
CO
空白 O3/CO=0.86 100℃
Institute for Thermal Power Engineering 浙江大学热能所
O3 with NO, SO2 reactions
0.0 0.2 0.4 0.6 0.8 1.0 1.20
50
100
150
200
NO SO2c
oncentration [ppm]
O3/NO molar ratio
100℃
• SO2 doesn’t have good performance like NO.
• How to improve the SO2 oxidization should be further studied.
Institute for Thermal Power Engineering 浙江大学热能所
0.862581
1.91
0.38
6289.31001.35Million300
By O3
21375kwTotal energy
6.33W/Nm3Average power consumption
100ppmNO removedKg/hO3 neededkW/kgO3O3 generated power
Kw/m3O2O2 generated power
300MWPower generated
7.13%
1.35Million
By Electro Beam
Nm3Flue gas
Power consumption by O3 at 300MW power plant