N2O Analyzer Certification to allow Carbon Trading fromallow Carbon Trading from Nitric Acid Plants under theKyoto ProtocolDr. Michael KamphusApplication Engineer

Dr. Achim DretzkeSenior Instrumentation Engineer

PresentersPresenters

Dr. Michael KamphusApplication Engineer for Process Gas Analyzer (PGA)Hasselroth, Germany

Dr. Achim DretzkeSenior Instrumentation EngineerSenior Instrumentation EngineerThyssenKrupp Uhde GmbHBad Soden, GermanyBad Soden, Germany

ThyssenKrupp Uhde: more than 2,000 plants worldwide

130 plants

Fertilisers RefineriesNitric acid Aromatics

185 plants 380 plants 75 plants

2,000 plants worldwide

115 plants375 plants120 plants

Org. Chemicals/petrochemicalsHydrogen, ammonia, methanol Plastics, synthetic fibres Polyester / polyamides

400 plants

105 plants500 plants150 plants

Electrolysis Coke Plant Technologies Tank storage facilities Industrial plants

150 plants105 plants500 plants150 plants 150 plants

W kf 5 600 ( 7 1 Mi i i h / )Workforce: ~ 5,600 (approx. 7.1 Mio engineering hours/year)

Analytical Division

Instruments

Analytical Division

AnalyzersInstrumentsLiquid Analytical

• pH/ORP

AnalyzersGas Chromatographs

• ProcesspH/ORP• Conductivity• Amperometric• Turbidity

Process• Natural Gas BTU

Process Gas Analyzersy• Wet Chemistry

Combustion

y• Process Gas• Hydrocarbons• CEMS

• In-situ O2• Extractive O2• CO

Systems and Services• Systems Integration

S i• Service• TrainingNet Safety

Fl / fi d t ti• Flame / fire detection• Smoke / oil mist detection• Combustible gas detection• Leak detection• Leak detection

IntroductionIntroduction

N2O Facts Global Warming & Kyoto Protocol EN14181 - QAL1: Type Approval of N2O Gas Analyzer UHDE EnviNOx® Process UHDE EnviNOx Process Instrumentation / Analytics / Control

E iNO ® W ld id EnviNOx® Worldwide Information Resources

N2O - FactsN2O Facts

Nitrous Oxide, “Laughing gas“ Natural and human-related sources

– Agricultural soil management– Animal manure management– Sewage treatment– Mobile and stationary combustion of fossil fuel– Adipic acid production– Nitric acid production

EPA identified 6 greenhouse gases which "may endanger public health or welfare." CO2, CH4, N2O, HFCs, PFCs & SF6

Global Warming GasesGlobal Warming Gases

Concentration 2005

Change since 1998

Radiative forcing 2005 (W/m2)

Lifetime(years)

Radiative efficiency (W/m2 ppb)

Global warming potential

CO2 379 ppm + 13 ppm 1.66 1.4E-5 1

CH4 1774 ppb + 11 ppb 0.48 12 3.7E-4 21

N2O 319 ppb + 5 ppb 0.16 114 3.03E-3 310

Kyoto ProtocolKyoto Protocol

U it d N tiUnited NationsFramework Convention on Climatic Change (UNFCCC)

Kyoto Mechanisms:Emissions Tradingss o s ad g CDM: Clean Development Mechanism

The CDM allows emission-reduction projects in developing countries to earn certified emission reduction (CER) credits.

JI: Joint ImplementationTh JI h i ll t ith i i d tiThe JI mechanism allows a country with an emission reduction or limitation commitment (Annex B Party) to earn emission reduction units (ERUs) from an emission-reduction or emission removal project in another Annex B Party.

CDM – MechanismTrading with emission certificatesTrading with emission certificates

Annex B CountryAnnex B Country(e.g. Germany)

Non-Annex B Country(e g Chile)(e.g. Chile)

CDM GuidelinesCDM Guidelines

M th d l i Methodologies– AM0028: “Catalytic N2O destruction in the tail gas of Nitric Acid

or Caprolactam Production Plants”or Caprolactam Production Plants– ACM0019: “N2O abatement from nitric acid production”

Describes the abatement technique and the requirements (whichDescribes the abatement technique and the requirements (which measurements, principle of measurement, parameters to be recorded, calculation, reporting, etc.)

Approved tools“T l t d t i th fl f h i– “Tool to determine the mass flow of a greenhouse gas in a gaseous stream”

– “Tool to calculate project or leakage CO2 emissions from fossil p j g 2fuel combustion.”

Binding guidelines for CDM projects!Binding guidelines for CDM projects!

N2O emissions monitoring systemN2O emissions monitoring system

Certified to meet or exceed the requirements of the prevailing best industry practice or monitoring standards in terms of operation maintenance and calibrationoperation, maintenance and calibration.

The latest applicable European standards and norms EN14181or equivalent standards, which prescribes the features needed q pfor Automated Measuring Systems (AMS) need and how they are to be calibrated and maintained, shall be used.

– AI: measurement for the concentration of N2O EN14181– FI: measurement for total flow rate EN14181FI: measurement for total flow rate EN14181– PI: measurement for pressure– TI: measurement for temperature

EN14181 - QAL1EN14181 QAL1

EN14181 St ti i i Q lit f EN14181: Stationary source emissions - Quality assurance of automated measuring systems (AMS)AMS consists of a complete system from sampling probe to

l i l di l h dlianalyzer including sample handling

QAL1• Suitable AMS• EN 15267-3

QAL2• Correct Installation & Calibration• Standard Reference Methods

QAL3 / AST• Continuous

Functionality• Type Approval

EN 15267-3: Air quality - Certification of automated measuring systems - Part 3: Performance criteria and test procedures forsystems Part 3: Performance criteria and test procedures for automated measuring systems for monitoring emissions from stationary sourcesQAL = Quality Assurance LevelAST = Annual Surveillance Test

EN 15267-3EN 15267 3

T i d d t AMS t t d i l b t d fi ldTwo independent AMS are tested in laboratory and field Lack of fit Biggest interference (15% CO2, 3% O2, 20 mg/m3 CO, …)gg ( 2 2 g ) Span shift in field test Zero shift in field test Sensitivity to sample volume flow Sensitivity to sample volume flow Sensitivity to sample pressure Sensitivity to sample temperature

S iti it t bi t t t Sensitivity to ambient temperature Dependence on supply voltage Repeatability at spanp y p Field reproducibility Uncertainty of test gas reference point

Total expanded uncertainty < 20% of range

Laboratory TestingLaboratory Testing

TUV Rheinland in Cologne 4 weeks laboratory testing of both

AMS including 30 m 130 oC heated sample gas line

Sample handling system to cope with build up of ammonium nitrate crystals p yduring startup and shutdown of process

Field TestingField Testing

Adipic Acid plant in Zeitz (East of Germany) Measurement of N2O in flue gas2

Duration approx. 3 month (until Sep 2012) TUV Rheinland is testing drift reproducibility linearity TUV Rheinland is testing drift, reproducibility, linearity

and comparison to reference method during 10 visits at siteat site

EnviNOx® ProcessEnviNOx ProcessTail Gas with N2O and NOx

Ammonia

EnviNOx®

Reactor(EnviCat®)

Hydrocarbon

(EnviCat®)

Efficiency:Efficiency:> 97 %

Clean Tail Gas

N2O reduction of up to 99+ %NOx removal down to ~ 0 ppmv

Why do Plant Owners Invest in EnviNOx® ?EnviNOx ?

N2O emissions of a nitric acid plantT il fl 130 000 N ³/hTail gas flow: 130,000 Nm³/h

N2O concentration: 1,000 ppm

→ N2O flow: 130 Nm³/h255 kg/h

Global Warming Potential of N O = 310Global Warming Potential of N2O = 310

CO2-equivalents: 79,134 kg/h0.6 Mio. CER/year

3 Mio. US$/year

• Local emission standards(EU: 20-100 ppm, 300 ppm for existing plants)

• Carbon trading (Kyoto protocol)

• Reputation / Marketing (“saving the environment”)Reputation / Marketing ( saving the environment )

Requirements on Analyzer and Instrumentation PackageInstrumentation Package

Process• Safe operation of process• Safe operation of process• Control of ammonia and

hydrocarbon• Measurement and recording of

process parameter

CDM (UNFCCC)• Reliable measurement process parameter• Measurements (N2O and

volume flow) QAL1 certified acc. to EN14181

• Validation after installationValidation after installation (QAL2) and in running plant (QAL3)

• Regular maintenance• Tamper proof data recording• Tamper-proof data recording

and storage• Availability of long term data

historyT bilit f fi ti

Implementation• Stand-alone system• To be integrated in existing

• Traceability of configuration changes

• Restricted access to measuring and data storage

t To be integrated in existing plant

• Well-defined interfaces

system

Requirements on Supplier for Analyzer and InstrumentationAnalyzer and Instrumentation

Equipment The equipment shall fulfil all requirements from process

and UNFCCC

Project Execution Single supplier for all parts of instrumentation and control One responsible person for all disciplines Support on site (start-up) Support for customer (maintenance, trouble shooting,

service agreement) Feed back to Uhde

E t f E iNO ®Emerson as a partner for EnviNOx®

Emerson’s Contributions to Uhde EnviNOx® ProjectsEnviNOx Projects

Supply of equipment (analyzer, sample handling, analyzer container, control system, field instruments)y )

Programming of control system (DeltaV) Programming of data recording and reporting software Programming of data recording and reporting software

(DeltaV)S t d i t t Support during start-up

Regular maintenance Trouble shooting Supply of spare partspp y p p Service contract with Uhde customer

EnviNOx® - A Living SystemEnviNOx A Living System

Each project is individual Different scope (depending on Uhde client)

Design changes by Uhde Design changes by Uhde Third party emission monitoring system instead of DeltaV Location of sampling point (→ sample preparation has to Location of sampling point (→ sample preparation has to

be modified) …

Requirements from UNFCCC are changingC f f (Q 1 1 181) Certification of analyzers (QAL1, EN14181)

Reporting Documentation / certification Documentation / certification …

Instrumentation for Ammonia / Hydrocarbon DosingHydrocarbon Dosing

FT: Coriolis Micro Motion FFT: Coriolis Micro Motion FPT: Rosemount 3051TT: Rosemount 248TT: Rosemount 248PI: Wika 232.50XV / FV: Fisher GX

safe l ti

XV

location

Ammonia /TT

FTPTPI

Ammonia / Hydrocarbon

XV FV

Instrumentation for Tail Gas LineInstrumentation for Tail Gas LinePT: Rosemount 3051TT: Rosemount 248FT: Venturi acc. ISO5167-4

Tail GasTT

FTPT

Analytics - Sample HandlingAnalytics Sample HandlingPrimary sample h dlihandling

Analyzer container

Trace heated l lisample line

Sampling point

Analytics - Sample Handling and Analyzer (inside Container)Analyzer (inside Container)

MLT 2Dual compartmentFi ld h iField housing

EnviNOx® Inlet

N O: 0 2000 ppm

EnviNOx® Outlet

N O: 0 100 ppmN2O: 0..2000 ppm

NO: 0..300 ppm

N2O: 0..100 ppm

NOx: 0..50 ppm

NO2: 0..300 ppm CH4: 0..100 ppm

O2: 0..5 %

EnviNOx® ContainerEnviNOx Container

H i f Housing for– Analyzer– Sample handling– Calibration gases– Control system

Equipped withq pp– HVAC– Power supply– Instrument air supplypp y

Completely installed andtested at factory

easy start up on site→ easy start-up on site Clean and safe environment for maintenance work Access can be restricted (CDM requirement), unmanned during ( q ), g

normal operation

Control SystemControl System

Optical fiber

Analyzer container Control room

Control SystemControl System

DeltaV Process control

D t it i Data monitoring Data storage

R ti Reporting

HIMatrix F35HIMatrix F35 Safety related process control

Personal Computer Operator station Operator station Engineering station Back-up station Back up station

EnviNOx® WorldwideEnviNOx Worldwide

UhdUhde EnviNOx®

UhdUhde EnviNOx®

with Emerson package

EnviNOx® plants with Emerson equipmentequipment

Carbon Projektentwicklung GmbH (2007)Carbon Projektentwicklung GmbH (2006) j g ( )Hu-Chems Plant No. 4Location: Yeosu, Rep. of KoreaCapacity: 1,150 t/d nitric acid

j g ( )Abu Qir IILocation: Alexandria, EgyptCapacity: 1,830 t/d nitric acid

Volume flow: 150,000 Nm³/hReduction: 0.62 million t CO2e/y

Volume flow: 233,000 Nm³/hReduction: 1.4 million t CO2e/y

Carbon Projektentwicklung GmbH (2007)Hu-Chems Plant No. 3Location: Yeosu, Rep. of KoreaC it 300 t/d it i id

Carbon Projektentwicklung GmbH (2007)Hu-Chems Plant No. 2Location: Yeosu, Rep. of KoreaC it 300 t/d it i idCapacity: 300 t/d nitric acid

Volume flow: 41,000 Nm³/hReduction: 0.33 million t CO2e/y

Capacity: 300 t/d nitric acidVolume flow: 41,000 Nm³/hReduction: 0.33 million t CO2e/y

Nitrogénművek Zrt. (2007)Location: Pétfürdő, HungaryCapacity: 1 500 t/d nitric acid

Omnia Fertilizer Ltd (2007)Location: Sasolburg, South AfricaCapacity: 750 t/d nitric acidCapacity: 1,500 t/d nitric acid

Volume flow: 202,000 Nm³/hReduction: 0.99 million t CO2e/y

Capacity: 750 t/d nitric acidVolume flow: 95,000 Nm³/hReduction: 0.58 million t CO2e/y

EnviNOx® plants with Emerson equipmentequipment

Enaex S. A. (2007)Location: Mejillones, ChileC /Capacity: 925 t/d nitric acidVolume flow: 122,000 Nm3/hReduction: 0.93 million t CO2e/y

Fatima Fertilizers Comp. Ltd. (2009)Location: Rahim Yar Khan, PakistanCapacity: 1,500 t/d nitric acid

Total reduction of all running

EnviNOx® plantsCapacity: 1,500 t/d nitric acidVolume flow: 195,000 Nm³/hReduction: 0.99 million t CO2e/y around 10 million t CO2e/y

70% ith E i tOmnia Fertilizer Ltd (2012)Location: Sasolburg, South AfricaCapacity: 1,000 t/d nitric acidVolume flow: 130 000 Nm³/h

70% with Emerson equipment

Volume flow: 130,000 Nm³/hReduction: 0.79 million t CO2e/y

SummarySummary

N O h l b l i ff N2O has a strong global warming effect UNFCCC mechanisms to trade emission certificates from

destroyed N Odestroyed N2O UHDE’s EnviNOx® reactor is an efficient process for

removing N2O from nitric acid / caprolactam plant emissionremoving N2O from nitric acid / caprolactam plant emission Process Gas Analyzer and Flow Measurement have to be

certified according to EN14181 A complete package from one supplier helps UHDE to

minimize project effort10 CO / O ® Up to now 10 Mio t CO2e/y are saved with the EnviNOx®

process For a mid size nitiric acid plant certificates worth 3 Mio For a mid size nitiric acid plant certificates worth 3 Mio

US$/year can be traded

Where To Get More InformationWhere To Get More Information

Kyoto Protocol: www.unfccc.int

UHDE EnviNOx® : www.uhde.eu/