Transcript Zero emission power plants” Torsten Strand

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“Zero emission power plants”
Torsten Strand
27/04/2020
Power Generation
1
Content
 Introduction
 What is a zero emission plant?
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 No NOx and no CO2 emissions?
 Using a renewable fuel?
 Some technologies for NOx reduction
 combustion modifications
 clean up systems
 Some different technologies for CO2 capture
 combustion modifications = oxidation of fuel
 mixed conducting membranes
 chemical looping
 absorption
 fuel modifications
 Combinations of NOx reduction and CO2 capture
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Power Generation
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What is the best way to reduce CO2
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 In the global perspective the power industry seems to be able to
prove that efficiency improvement in power production is enormously
more important than
 Change of fuel
 CO2 sequestration
 What do you think???
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Power Generation
3
Coal fired steam turbine plants
 The efficiency of such plants have a wide range going from
 a small back pressure plant e = 24 % tot = 90%
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 An advanced high pressure condensing plant with three pressure levels
and double reheat
e = 46 % tot = 46%
 The next step is coal gasification with a gas turbine + steam turbine in combined
cycle, but this step has not been really commercial in spite of many years of R&D
 The hope for the “gasification club” is now to combine gasification with
synthetic fuel production
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Case 1
Gas Turbine in Simple Cycle
63.6 % losses
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Gas Turbine
36.4 % electricity
100 % fuel
Pgt
Pst
Paux
Pnet
Heat duty
Qfired
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44.30
0
0.10
44.20
0
121.4
MW
MW
MW
MW
MJ/s
MJ/s
Alfa
 --Net electrical
Powerefficiency
Generation 36.4 %
Net total efficiency
36.4 %
5
Case 2
Gas Turbine in Cogeneration Cycle
12 % losses
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1-pressure HRSG
52.2 % process heat
Gas Turbine
35.9 % electricity
100 % fuel
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Pgt
Pst
Paux
Pnet
Heat duty
Qfired
Alfa
NetPower
electrical
efficiency
Generation
Net total efficiency
43.82
0
0.23
43.59
63.4
121.4
MW
MW
MW
MW
MJ/s
MJ/s
0.69 --35.9 % 6
88.1 %
Case 3
Gas Turbine in Combined Cycle
Steam Turbine
(condensing)
12 % losses
520 deg C
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2-pressure
HRSG
31 deg C
16.8 %
electricity
31 deg C
15 deg C
Gas Turbine
100 % fuel
Pgt
Pst
Paux
Pnet
Heat duty
Qfired
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27 deg C
35 % losses
35.9 % electricity
Alfa
Net electrical efficiency
Net total efficiency
43.69
20.78
0.70
63.77
0
120.9
MW
MW
MW
MW
MJ/s
MJ/s
 --52.7 %
52.7 %
Power Generation
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Case 4
Gas Turbine in Combined Cycle
Steam Turbine
(district heating)
11 %
losses
11.3 %
electricity
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510 deg C
2-pressure
HRSG
78 deg C
42.1 %
heat
90 deg C
Gas Turbine
60 deg C
35.9 %
electricity
100 % fuel
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78 deg C
Pgt
Pst
Paux
Pnet
Heat duty
Qfired
43.70
14.18
0.62
57.26
51.1
121.4
MW
MW
MW
MW
MJ/s
MJ/s
Alfa
1.12 --Powerefficiency
Generation 47.2 %
Net electrical
Net total efficiency
89.3 %
8
What is a zero emission power plant
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 Power plant emissions can be
 Unwanted content in the exhaust gas (CO2, NOx, CO, VOC, SO2, dioxin,
smoke, particles, steam plume…..)
 Ash, cooling water, spill water, lube oil
 Noise and vibrations
 Transports of fuel and ash, fuel preparation
 In a Zero emission power plant
 all emissions but CO2 are low as a result of good engineering required by
laws, directives and regulations
 Some claim that the emissions from transport and preparation of fuels is not
considered in the right way when making assessment of different technologies
 Is a bio mass fueled plant CO2 free?
 It was anyway considered CO2 neutral in many countries
 up to some weeks ago when it was shown that forests produce methane
 Is CO2 sequestration from a bio mass fuel plant unnecessary?
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The bio fuels = CO2 neutral fuels
 Today’s sorted municipal waste and biomass are rather similar when
seen as an energy source
 Heating value

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Waste:
 Wood chips:

5 -17 MJ/kg (oil has 44 HJ/kg)
18 MJ/kg
Contain corrosive elements

Waste:alkali metals, ammonia, chlorides, metal vapors
 Biomass:
alkali metals, ammonia

Power production from bio mass is low, mostly only heating

Ways for power production
 Bio mass fired boilers with steam production for steam turbine
 Bio mass fired gas turbine with exhaust boiler and steam turbine
 Bio mass gasification + gas turbine with exhaust boiler and steam
turbine
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The new boiler at Garstad
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The original incineration boiler
1.
2.
3.
4.
Waste
dump
Crane
Grate
Fan
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5. Ash cooler
9. Electrostatic particle filter
6. Steam generator
10. Scrubber
7. Exhaust gas recirculation 11. Cooler
8. Urea injection
12. Air preheater
13. Water treatment
14. Ca +ash injection
15. Textile filter
16. Fan
17. Stack
Power Generation
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Bio mass boiler with gas turbine as
fan for combustion air
Wood powder fired gas turbine for production
of hot combustion gas for the bio mass boiler
Enakraft project in Enköping
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Power Generation
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Bio oils & alcohols

Will bio oils or alcohols ever become a fuel for electricity production?
 A 15 MW gas turbine will consume almost all rape seed oil that is
produced in Sweden
 Palm oil is one of the best candidates, since it is really not suitable
for use in food

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But the palm oil plantations are said to ruin land in the Far East and
China!!
 Palm oil can be refined to different levels of purity. Rather crude palm oil
has been used in diesel engines
 Refined palm oil can be burned in gas turbines

Ethanol from cane sugar industry has off and on come up as a gas
turbine fuel in Brazil, but now it will be all consumed in cars

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Ethanol can be burned in gas turbines
Power Generation
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Black liquor
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 Black liquor is a byproduct in the pulp industry
 Contains lignin and cellulose fibers by also all the alkali metals
concentrated, which makes it very corrosive when fired
 The Soda boilers are producing low temperature steam which is not
so good for electricity production in steam turbines
 Gasification of black liquor has been a topic for year:
 Gasify and wash the gas from alkali and ammonia
 Burn in a high efficiency combined cycle
 Lately the focus has shifted to
 Gasify and make DME for replacement of diesel in transport sector
 Burn the rest
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Synthetic air based fuel process with
integrated gas turbine (Syntroleum)
GTX100 in Syntroleum Process
NG
ATR
FTR
IC3
H
Sepa
rator
Cont
roller
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NG
IC
2
Steam
G
GC
HPC
C
o
m
bu
st
or
HPT
LPT
LPC
IC
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Syntroleum process gases
Synthetic gas after ATR
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N2
CO2
CO
H2
C1
H2O
Vol. %
Typical Range
45.61
2.50
17.04
33.32
0.09
39 - 48
2.3 - 2.7
16 - 18
31 - 33.5
0.08 - 0.1
1.44 1 - 2.5
Tail gas for GT fuel
N2
CO2
CO
H2
C1
C2+
H2O
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Vol. %
Typical Range
82.86
4.76
4.64
4.78
1.86
0.79
0.31
83 - 79
4.7 - 6.0
4.2 - 6.0
4.7 - 5.0
1.8 - 3.0
0.6 - 1.1
0.25 - 0.4
Power Generation
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Fossil fuels
 The fossil fuels are more or less dirty and contains more or less carbon
 Coal is worst
 high Carbon content
 high content of metals and Sulpher
– Can be cleaned before combustion
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 Oil is better
 Lower Carbon content C/H  6.5
 Low content of metals and Sulpher
– Which is today removed before combustion
 Natural gas
 Still lower Carbon content C/H  3
 Very little metals and Sulpher
 Industrial off gases
 Content varies from high H2 to high CO
 Often very dirty but can be cleaned before combustion
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Basics on NOx
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 NO and NO2 are produced when a small amount of the N2 in the air is
passing through a flame
 There are two types of NOx = NO + NO2
 Promt NOx, produced in the flame front, proportional to pressure
 Thermal NOx, produced at high temperature in the post flame flow.
Thermal NOx is exponentially proportional to temperature and
proportional to residence time
 The rate of NOx is thus proportional to pressure and residence time and
exponentially increasing with flame temperature
 Generally NO2 is produced a lower flame temperature, NO at higher
 NO2 can at high concentrations look like yellowish smoke
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Turbine Inlet Temperature
TIT C
1500
NOx ppmv
200
Ceramics
Single Crystal Blades
Steam Cooling
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GTX100
Jet Engines
GT10
1000
100
GT35
Stationary Gas Turbines
NOx
500
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1940
1960
1980
- Trends -
2000
Year
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Combustion conditions
 The main combustion parameters are increasing with gas turbine power
 combustion air flow, temperature and pressure
 turbine inlet temperature
 fuel flow and fuel/air ratio
resulting in an increasing
 flame temperature
Flame temperature = f( fuel/air ratio, air temp, humidity, fuel composition)
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- Flame temperature -
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Nitric Oxide Formation
NOx
200
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Water Injection
100
Lean Premix
Combustion
0.5
Steam Injection
1.0
1.5
Fuel/Air Equivalence Ratio
Power Generation
- NOx is reduced by cooling down the flame
with H2O -
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NOx and CO vs Flame Temperature
NOx ppm
CO ppm
EV Burner
DLE Gas
AEV Burner
DLE Gas & Oil
50
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NOx
40
40
30
30
CO
Low oxygen burner20
20
Catalytic burner
10
10
1700
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1800
Flame Temp K
1900
- Advanced DLE burners Power
- Generation
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One Next step: Flame less combustion
 The basic philosophy is as with exhaust gas recirculation in boilers
 If exhaust gases are mixed with the combustion air O2 is reduced,
which reduces flame temperature further
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 The thinking is that the recirculation of combustion gases to the
combustion zone can be done within the combustor, using clever
aerodynamics
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Another way: Catalytic Combustion
Fuel
injector
Combustion
chamber
1st stage 2nd stage
catalyst catalyst
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Preburner
&
mixer
T (compressor
discharge) =
350 - 500 °C
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T(in, cat)
> 500°C
T (1,out)
T (2,out)
> 750°C 850<T<1000°C
T (hot gas)
ca. 1300 °C
Powersurfaces
Generation - Low temperature reactions on catalytic
25
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Exhaust gas clean up
 Selective Catalytic Reactor
 Ammonia is mixed into the combustion air after the gas turbine
 In the catalytic reactor the ammonia reacts with NOx to produce N2
and H20
 90% efficiency
 Works between certain temperature limits, thus has to be
positioned in an exhaust gas boiler
 Ammonia slip is a problem
 Ammonia has to be controlled against NOx
 CH3 is almost as bad as CH4
 Deterioration of catalytic elements: average 6 years life
 SCR is most often combined with a DLE combustion system to
reach NOx levels around 3-5 ppm (+ 3ppm CH3 slip)
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NOx absorption
 The SCONOX system uses catalytic absorption
 The absorption elements works at lower temperatures than the SCR
 They are regenerated with H2 to form H20 and N2
 The SCONOX reactor is built up of a number of elements with
individual dampers on each element, upstream and downstream
 The regeneration is an ongoing process in which elements are shut
off by the dampers and blown by H2 for a minute
 The H2 is generated from the fuel gas by a steam reformer
 95 – 97% NOx removal efficiency
 ~ 4 times more expensive than SCR but there is a growing market in
the US, perhaps Norway and Japan
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CO2 emissions from man
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Zero emission power plants
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 Power plants with no NOx and no CO2 emissions
 CO2 recovered for sub surface re-injection in e.g. oil wells, porous
rock caverns, coal seams or deep sea
 the technologies are presently developed for natural gas, but the
main focus is on coal (combustion gas or gasification gas fuel)
 Technologies for CO2 recovery
 Fuel treatment, conversion to H2 and CO2
 Absorption with amides of fixation by bio chemistry
 Oxidation of fuel by oxygen in inert atmosphere
external oxygen source, oxidation in steam or CO2
mixed conducting membrane
chemical looping
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CO2 storage
 European Potential for Geological Storage of CO2 from Fossil Fuel
Combustion (GESTCO) mainly as compressed CO2 (liquid)
 onshore/offshore saline aquifers with or without lateral seal;
 low enthalpy geothermal reservoirs;
 deep methane-bearing coal beds and abandoned coal and salt mines
 exhausted or near exhausted hydrocarbon structures (oil and gas fields)
 In Japan the focus is on deep sea storage
 ongoing tests outside Hawaii of liquid CO2 at >2000 m depth
 In Canada storage of solid CO2 in the form of carbon silicate is tested
 CO2 injection in coal seems to drive out methane gas and reduce explosion
risk
 CO2 re-injection in oil fields for enhanced oil production
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CO2 storage in North Sea oil well
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The Canadian process for
solidification of CO2
 Anaerobic gasification of coal to H2 and CO2
 Combustion of H2 in Solid Oxide Fuel Cell
 Solidification of CO2 to calcium carbonate with lime
 Recovery of lime and release of pure CO2 using waste heat from the
SOFC
 Formation of magnesium carbonate from magnesium silicate
 Magnesium carbonate is stable and will be stored in the magnesium
silicate mines
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Fuel conversion
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 Presently natural gas CH4 can be converted to H2 and CO2 in a steam
reforming process.
 the conversion rate is around 80 - 90%.
 the steam converter can be placed in the gas turbine exhaust duct
 present gas turbine combustion technology can be used
 diffusion burners with steam injection for NOx reduction and burner
protection
 the H2 rich gas must leave the injector at a velocity high enough to
prevent the flame to move back to the injector
 Membrane technologies for H2 separation from natural gas is being
developed using ATR (Auto Thermal Reforming) combined with CO shift and
absorption with Selexol
 combustion technology for 100% H2 has to be developed
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Oxy-combustion
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 Combustion of a fuel, hydrocarbon or pure H2 with Oxygen, O2, without the
presence or air is called Oxy-combustion
 Several project ongoing to develop combustion technology for combustion in
inert gases, such as
 Steam
Air separation
plant
 CO2
Oxygen
Air
intake
CO2
to storage
CO2
compression
Cooling
water
Fuel
Combustor
Turbine
H2O
Recuperator
Condenser
Excess
water
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Coal conversion
 Coal will be burnt as today in large steam plants, but with CO2 sequestration
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 Coal gasification Combi Cycles are built today
 addition of CO2 recovery processes are now being developed
 Coal gas (the gas stored in the coal pits) will be used more frequently
 for reducing risk of explosions
 reducing need for ventilation
 Coal gasification underground is being developed in Russia
 a gas similar to coke oven gas (Hydrogen rich) is produced for use in
 combined cycles for power production
 in processes for liquid fuel production, with the rest product (lean gas)
used in the combi cycle
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CO2 injection in coal seams
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 Coal Bed Methane, CBM, is always leaking more or less from coal seams,
going into the atmosphere. It is also causing high explosion risks at mining
 Injection of CO2 in the coal beds is now tested to
 drive out the methane in a controlled way
 burn it in gas turbines
 recover the CO2
 re-inject the CO2
 Most of these processes require a catalytic process to produce H2 and
CO from the fuel gas
 The H2 and CO can then be burnt in inert atmosphere or converted to a
liquid fuel in another catalytic process
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CO2 absorption
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 The CO2 in combustion gas is absorbed in an amine solution which can be
re-generated. The amine solution is volatile and there is quite a large
consumption in atmospheric reactors. The amines are not fully
environmentally acceptable
 atmospheric absorption processes are developed for exhaust gas from
natural gas fired gas turbines and coal boilers. The CO2 concentration is low
and the plants large, since they have to handle big volume flows
 pressurised absorption has been suggested but so far not tested. There are
advantages
 the flow volumes are smaller
 the CO2 partial pressure higher
 the volatility of the amines is reduced and the losses smaller
 It is claimed that all components for the absorption systems are available on
the market
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Pressurised CO2 absorption
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 Two cycles have been suggested
 absorption reactor after the combustor at highest pressure and
temperature
 absorption reactor in between turbines at lower pressure and
temperature
 The absorption process generally reduces a combined plant efficiency by
more than 10% mainly due to pressure losses
 a special cycle similar to the PFBC cycle, but with gas fired combustor would
have lower initial efficiency, but will have less influence of the absorption
system
 in order to further reduce the absorption system gas turbines are used in
series
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Pressurised CO2 absorption system
 The P-type gas turbine has a pressurised gas fired steam generator of the same
basic design as a PFBC. The exhaust gas is cooled down to ~ 100°C before going
in to the CO2 absorption vessel. The gas is then reheated before going to the
turbine. NOx is hopefully washed out in the cooling process.
CO2
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Pressurised steam generator
Pressurised amino
scrubber
950 C
Heat
exchangers
From High
Pressure
Compressor
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Name of Event
To steam
turbine
To High Pressure
Turbine 850 C
Power Generation
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17MW GT35P and 70 MW GT140P
Flexible gas turbines, adjustable for LBTU gases, with silo
type of LBTU combustor
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500 MW Plant configuration with CO2
concentration
#1&#2 step
GTX100
#3 step
HRSG
#4 step
Scrubber
Nock out pot
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GT140P
CO2
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Combi cycle with high pressure CO2
absorption using amine solution
To stack
Absorption of CO2 at pressure
HRSG
Air
intake
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after the combustor
Condenser
in between turbines
Steam
Fuel
favourable due to higher CO2
partial pressure
Exhaust
and atmospherically
Compressor
Steam
turbine
Turbine
Gas turbine
Compression
of CO2
1
Steam
bleed
CO2
CO2
6
5
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8
7
3
9
Loss in efficiency >10%
The use of two gas turbines in
series to increase CO2
concentration
2
4
after the turbine
only 3% CO2
2
Power Generation
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CO2 turbines
 Several cycles have been proposed using closed loop CO2 turbines
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 Unfortunately a standard gas turbine will not work due to the difference
in density and specific heat cp from air
 more stages in turbine and compressor
 Proposals for running the closed loop at high pressure to reduce the
plant size has been presented
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Plants for O2 production and power
plants with integrated O2 production
 Oxygen production using Mixed Conducting Membranes are being
developed. Oxygen will be needed for many gasification processes
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 In order to reduce size of the plants and especially the reactor, the plants are
pressurised by integrating a gas turbine.
 The next step is to use the same technology for power production
 The critical element is the Mixed Conducting Membrane itself and the reactor
built on it
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Membrane Transport
Processes
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 Generally, gas-selective membranes are based on porous
membranes that use the molecular size to separate gas
components in a mixture, e.g. Knudsen flow or molecular sieving
 Dense membranes (ceramic or metal) transport atoms or ions
selectively through the membrane
 Dense oxygen selective membranes transport both oxygen ions
and electrons, i.e. mixed conductivity
 Driving force gives that pO2, permeate < pO2, retentate
Sweep gas
Sweep gas +
O2
pO2, permeate
e-
pO2, retentate
N2 + less O2
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O2-
Dense ceramic
mixed conductive
membrane
N2+ O2 (usually air)
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Oxygen flux (permeability) is a
function of:
 Membrane material
 Temperature
(Arrhenius-type behavior)
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 Membrane thickness/thinness
 Potential Pressure gradient (pO2)
 Reported from others are:
 Balachandran: O2 permeability 2.5 cc cm-2 min -1,
that is 36 kg O2 m-2 per day
 Norsk Hydro: 200 kg O2 m-2 day-1
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Catalytic combustion membrane
system
The membrane can be integrated with a combustion catalyst to
combust the fuel on the surface of the membrane support. Hence
heat exchanger, membrane and catalyst is integrated into one module
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CH4
CO2+
H2O
O2
e-
N2 + less O2
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O2-
Porous Catalytic washcoat
(hexaaluminate?)
Porous Carrier
(modified alumina?)
Dense membrane
(perovskite?)
N2+ O2
Power Generation
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Membrane materials I - mixed ion/electron
conductors
Various membrane structures
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a) thin dense membrane layer on porous substrate
b) porous substrate plugged with dense membrane particles
c) thin dense membrane with increased surface area
A
B
C
Porous support
Dense membrane
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Early MCM Combustion System
H2O,CO2,O2
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Pre-combustor
CH4
Preheater
Membrane
After burner
Compressor Air
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H2
Turbine Inlet
Power Generation
50
Combustor
CH4
Membrane
Air Preheater
CH4
Compressor
HEX
Condenser
Combustor
CO2
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850 C/12 bar
Power Plant
Efficiency 37%
Gas Turbine
420 C
Boiler
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Steam Turbine
Power Generation
Early MCM Power Plant
51
CH4
Steam
Membrane
Reactor
Air Preheater
CH4
Combine Cycle
Efficiency 47 %
Start
Combustor
Water injection
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Steam Injection
1200 C/14 bar
CO2+H20
Gas Turbine
550 C
450 C
20 bar
Steam Turbine
Boiler
To Steam turbine
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CO2
Power Generation
Intermediate MCM Power Plant
52
CH4
Air Preheater
CH4
Combine Cycle
Efficiency 55 %
Start
Combustor
Steam Injection
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Steam
Membrane
Reactor
1200 C/14 bar
CO2+H20
Gas Turbine
550 C
1200 C
20 bar
Steam Expander
Boiler
To Steam turbine
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Final MCM Power Plant
CO2
Power Generation
53
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Chemical looping basics
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Power Generation
54
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Chemical looping with fluid beds
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Power Generation
55
Fuel Cell
 The Solid Oxide Fuel Cell is very similar to the Mixed Conducting Membrane.
 In MCM the ion/electron transport is Short circuited
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 in the SOFC membrane there is electrical leads on the membrane to use the
electron transport
 in the fuel cell power plant around 60 - 80% of the electric power will be
produced in the membrane and the rest from the turbines. The gas turbine will
be small and is there mainly to pressurise the system and circulate the
medium.
 the development of Solid Oxide fuel cells has gone on for years, but without a
break through. Siemens is one of the few players.
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Conclusions
Siemens Power Generation 2003. All Rights Reserved
 The power production cycles for the future will have gas and/or steam
turbines integrated in the processes
 There will be a number of gas turbine applications for low heating value gases
 bio mass gasification
 off gases from chemical processes and steel industry
for which special combustion systems must be developed
 lean premixed systems
 catalytic systems
 CO2 sequestration will be applied to all power production independent on fuel
origin (fossil or bio mass)
 processes with membranes will probably be the best but absorption type
of clean up systems are closer to realisation
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Power Generation
57
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Please address all correspondence to:
Siemens Industrial Turbomachinery AB
SE-612 83 FINSPONG
© Siemens Industrial Turbomachinery AB
No part of this document may be reproduced or transmitted in any form or by any means, including
photocopying and recording without the written permission of Siemens Industrial Turbomachinery AB
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Power Generation
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