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“Zero emission power plants”Torsten Strand

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Content

Introduction What is a zero emission plant?

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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What is the best way to reduce CO2

In the global perspective the power industry seems to be able to prove that efficiency improvement in power production is enormously more important thanChange of fuelCO2 sequestration

What do you think???

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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% 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 1Gas Turbine in Simple Cycle

100 % fuel

Gas Turbine

63.6 % losses

36.4 % electricity

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100 % fuel

1-pressure HRSG

Gas Turbine

Case 2Gas Turbine in Cogeneration Cycle

12 % losses

35.9 % electricity

52.2 % process heat

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Steam Turbine (condensing)

100 % fuel

15 deg CGas Turbine

Case 3Gas Turbine in Combined Cycle

2-pressure HRSG

520 deg C

27 deg C

31 deg C31 deg C

12 % losses

35.9 % electricity

16.8 % electricity

35 % losses

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100 % fuel

Gas Turbine

Steam Turbine (district heating)

90 deg C

60 deg C

2-pressure HRSG

Case 4Gas Turbine in Combined Cycle

510 deg C

78 deg C

78 deg C

11 % losses

35.9 % electricity

11.3 % electricity 42.1 %

heat

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What is a zero emission power plant

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 Waste: 5 -17 MJ/kg (oil has 44 HJ/kg)Wood chips: 18 MJ/kg

Contain corrosive elementsWaste: alkali metals, ammonia, chlorides, metal vaporsBiomass: 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. Waste dump

2. Crane3. Grate4. Fan

5. Ash cooler6. Steam generator

7. Exhaust gas recirculation8. Urea injection

9. Electrostatic particle filter 10. Scrubber11. Cooler12. Air preheater

13. Water treatment14. Ca +ash injection15. Textile filter16. Fan17. Stack

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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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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 foodBut 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 enginesRefined 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

Ethanol can be burned in gas turbines

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Black liquor

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)

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Syntroleum process gases

Synthetic gas after ATR

Tail gas for GT fuel

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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 contenthigh content of metals and Sulpher

– Can be cleaned before combustion

Oil is betterLower Carbon content C/H 6.5Low content of metals and Sulpher

– Which is today removed before combustion

Natural gasStill lower Carbon content C/H 3Very little metals and Sulpher

Industrial off gasesContent varies from high H2 to high COOften very dirty but can be cleaned before combustion

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Basics on NOx

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

- - TrendsTrends - -

1940 1960 1980 2000

1000

1500

500

Jet Engines

Stationary Gas Turbines

Single Crystal Blades

GT10

GT35

GTX100

Year

Ceramics

Steam Cooling

100

200

NOx ppmvTIT C

NOx

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Combustion conditions

- - Flame temperatureFlame temperature - -

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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Nitric Oxide Formation

- - NOx is reduced by cooling down the flame with H2O -NOx is reduced by cooling down the flame with H2O -

200

100

0.5 1.0 1.5

Fuel/Air Equivalence Ratio

Water Injection

Steam InjectionLean Premix Combustion

NOx

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NOx and CO vs Flame Temperature

- - Advanced DLE burners -Advanced DLE burners -

10

20

30

40

50

1700 1800 1900 Flame Temp K

NOx ppm

CO

40

30

20

10

CO ppmEV BurnerDLE Gas

NOxAEV BurnerDLE Gas & Oil

Low oxygen burner

Catalytic burner

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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

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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Preburner &

mixer

1st stage catalyst

2nd stage catalyst

Combustion chamber

Fuel injector

T (1,out) > 750°C

T (2,out) 850<T<1000°C

T (hot gas) ca. 1300 °C

T (compressor discharge) = 350 - 500 °C

T(in, cat) > 500°C

Another way: Catalytic Combustion

- - Low temperature reactions on catalytic surfaces -Low temperature reactions on catalytic surfaces -

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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 NOxCH3 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

Power plants with no NOx and no CO2 emissionsCO2 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 CO2Absorption with amides of fixation by bio chemistryOxidation of fuel by oxygen in inert atmosphere

external oxygen source, oxidation in steam or CO2mixed conducting membranechemical 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

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

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 CO2

Fuel

CombustorAirintake

Air separationplant

Turbine

CO2 to storage CO2

compression

Oxygen

RecuperatorCoolingwater

Excesswater

H2O

Condenser

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Coal conversion

Coal will be burnt as today in large steam plants, but with CO2 sequestration

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 productionin 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

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

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

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.

Name of Event

Heat exchangers

Pressurised steam generator

Pressurised amino scrubber

CO2

To High Pressure Turbine 850 C

From High Pressure Compressor To steam

turbine

950 C

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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

GTX100 HRSG Scrubber

Nock out pot

GT140P

CO2

#1&#2 step #3 step #4 step

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Combi cycle with high pressure CO2 absorption using amine solution

3

1

24

5

67

8

92

Compression of CO2

Steamturbine

HRSGCondenser

To stack

Fuel

Compressor

Exhaust

Airintake

Turbine

CO2

CO2

Gas turbine

Steambleed

Steam

Absorption of CO2 at pressure

after the combustor

in between turbines

favourable due to higher CO2 partial pressure

and atmospherically

after the turbine only 3% CO2

Loss in efficiency >10%

The use of two gas turbines in series to increase CO2 concentration

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CO2 turbines

Several cycles have been proposed using closed loop CO2 turbines

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

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

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

N2 + less O2 N2+ O2 (usually air)

Dense ceramicmixed conductivemembrane

O2-e -

pO2, permeate

pO2, retentate

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Oxygen flux (permeability) is a function of:

Membrane material

Temperature (Arrhenius-type behavior)

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

CH4 CO2+ H2O

N2 + less O2 N2+ O2

O2

Porous Catalytic washcoat (hexaaluminate?)Porous Carrier (modified alumina?)Dense membrane (perovskite?)

O2-e -

The membrane can be integrated with a combustion catalyst tocombust the fuel on the surface of the membrane support. Henceheat exchanger, membrane and catalyst is integrated into one module

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Membrane materials I - mixed ion/electron conductors

Various membrane structuresa) thin dense membrane layer on porous substrateb) porous substrate plugged with dense membrane particlesc) thin dense membrane with increased surface area

A B C

Dense membrane

Porous support

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Early MCM Combustion System

H2O,CO2,O2

Pre-combustor

Preheater

Membrane

After burner

CH4

Compressor Air

H2

Turbine Inlet

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CombustorCH4

Membrane

CH4

Steam TurbineBoiler

Gas Turbine

Compressor

Early MCM Power Plant

HEX Condenser

CO2

850 C/12 bar

420 C

Combustor

Air Preheater

Power Plant Efficiency 37%

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Start Combustor

CH4

MembraneReactor

CH4

Steam Turbine

Boiler

Gas Turbine

To Steam turbine

Intermediate MCM Power Plant

450 C 20 bar

CO2

CO2+H20

Steam

Air Preheater

550 C

1200 C/14 barSteam Injection

Combine Cycle Efficiency 47 %

Water injection

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Start Combustor

CH4

MembraneReactor

CH4

Steam Expander

Boiler

Gas Turbine

To Steam turbine

Final MCM Power Plant

1200 C 20 bar

CO2

CO2+H20

Steam

Air Preheater

550 C

1200 C/14 barSteam Injection

Combine Cycle Efficiency 55 %

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Chemical looping basics

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Chemical looping with fluid beds

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Fuel Cell

The Solid Oxide Fuel Cell is very similar to the Mixed Conducting Membrane.

In MCM the ion/electron transport is Short circuited

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

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 systemscatalytic 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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Please address all correspondence to:

Siemens Industrial Turbomachinery ABSE-612 83 FINSPONG

© Siemens Industrial Turbomachinery ABNo 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