7rirl 9©n + syngas 2016 -...

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55E7 Johnson Mat tll f r

c°rporation

делает нашу жизнь более удобной

Euromel® - зарегистрированный товарный знак меламина, производимого на промышленных установках, лицензированных компанией «ЕВРОТЕХНИКА», ведущего поставщика технологии меламина с 1978, который является признанием высочайшего качества меламина, как следует из опыта лицензиатов и производителей, таких как Methanol Holding (Тринидад), QAFCO (Катар), Grupa Azoty (Польша), Zhong Yuan Dahua (Китай) и многих других.

ПОРТФЕЛЬ ТЕХНОЛОГИЙ КОМПАНИИ «ЕВРОТЕХНИКА»

Ф Меламин (из карбамида или аммиака)<* Технический углерод (все марки А5ТМ)Ф Параформальдегид (из метанола или ф&рмйяиняО

Пента»ритрит, НПГ# ТМП Ф Солнечная )н«ргетик| - аккумулироини« термической энергии

www.eurotecnica.it

PmB?1Small volume methanol co-production Johnson Matthey

_______ ____ ____________ Process Technologies

COx slip from front end makes enough UFC-85 for associated urea plant

Methanol Synthesis CO CH3OH

Methanation CO CH4 + h2o

Making methanol• Saves hydrogen• Lower inert (CH4) concentration entering syn loop

Katalco Formox

Simplification of UFC manufactureIj m T£1

Johnson MattheyProcess Technologies

UFC-85

Katalco Formox

Benefits

• Savings• Increase with methanol price• Increase as NG price falls• Increase with distance transported

• Opportunities• Sell UFC/CH20 to third parties• Supply more than one urea plant

(same site or close by)• Consume methanol made from gas on

more than one ammonia plant• Security of supply of UFC• Operability and reliability

• Methanol reactor* Can be bypassed• No effect on ammonia/urea OSF

• No increase in manpower• Minimal maintenance requirements

Katalrn

mMlXJJohnson М аШ ю у

Process Technologies

------------------- fI I I Nitrogen + Syngas 2016 \

Chairperson: Gianpetro Testa

Business Development Officer OVS Officine Valle Seriana

S.p.A.

Thiogro

• Incorporates elemental sulphur into urea fertiliser, providing plants with the sulphur nutrition they need

• Elemental sulphur is the most concentrated form of sulphur; it is a readily available and cost effective raw material

• Plants take-up sulphur nutrient in the form of the sulphate ion, bacteria must oxidize the elemental sulphur.

• To accelerate this oxidation process, Shell has developed a patented process which micronizes the elemental sulphur into fine particles of, on average, less than 40 microns

• Elemental sulphur oxidizes over time, across the crop growth cycle

• The Shell Thiogro technology safely and efficiently combines urea and sulphur into a stable emulsion which is then granulated to Urea-ES

< ® >

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4 | 02.03.20161 Nitrogen & Syngas, Berlin | Or Fianzrahe, Rafael Garcia

W b Th iogro thyssenkrupp Uhde Fertilizer Technology

vvny öutpnur-cnnancea ureav

Three main factors contribute to global

soil sulphur deficiency

k Increased use ofm sulphur-free

fertilizers

. Intensified^cropping systems

worldwide

l Reduction ofm sulphur dioxide

emissions A

Global soil sulphur deficit

Soil sulphur deficiencies are widespread globally

• India: At least 40% of India’s arable land suffers from varying degrees of S deficiency.

• China: 44% of arable land in 18 studied provinces is sulphur deficient

• Estimated 10 million tonnes of additional sulphur needs to be applied back into global soils each year to address the deficiency (2015)

• Even with numerous specialty and sulphur- enhanced products entering the market, fewer than2 million tonnes of additional sulphur are being supplied to soils

• For example, in India sulphur fertiliser production in India is -650,000 tpy, with a current soil sulphur deficit estimated at 1.6 million

Thiogro1»ij»i.Bhgi.i fm V» *w l iii«iiw iii< twai.«ii

Sulphur (million ton nos)

thyssenkrupp Uhde Fertilizer Technology

The Value of Sulphur-Enhanced Urea

1. Potential production cost savings

Thiogro

Replacing a portion of the urea liquor with lower-cost sulphur

Replacing some urea liquor with sulphur extends the urea liquor supply - thus, more urea or Urea-ES can be produced

Farmers require fewer tons of Urea-ES to get the same nutrient value - meaning a higher price may be charged without costing farmers more overall per hectare

Premium pricing potential based on agronomic results, improved handling properties and decreased transportation and application costs

The Value of Sulphur-Enhanced Urea - Potential Value to Fertiliser Producers -

Potential Economical Benefits Potential Operational Benefits

• Increased production • Increased production / production flexibility• Production cost savings • Existing UFT urea granulation plants can be• Premium pricing converted easily* Differentiation into additional products • Production increase without any change to the• Value added sulphur management for gas based upstream facilities

urea producers

Surplus urea

< S >thyssenkrupp

Uhde Fertilizer Technology

Urea +Elemental Sulphur

Thiog ro

The Value of Sulphur-Enhanced Urea• Potential Value to Farmers -

Potential Agronomic Benefits Potential Economical Benefits

Yield Increase Crop quality Improvements Higher nutrient density Balanced nutrients In a single granule

Reduced spreading operations Savings In fuel

offer farmers a balanced fertiliser option (N ♦ S) in a single granuleapplied in a single pass

which can easily be

46 2 %wt N

Thiogro

0 ft ©

a eO o o

• 0 - * © a

43-0-0 7S 40-0-0 13S 30-0-0 24S

ttvysMnkfupp

Urea-ES - Joint development by Shell and UFT

Shell UFT

• Extensive experience with the safe handling and • UFT and its predecessors have accumulated 35processing of elemental sulphur years of Know-how about fluidized bed Granulation

of Urea

• Ongoing major research and development • UFT operates a batch pilot plant for testing fertiliserprogram for Urea-ES including formulations in a fluidized bed granulator.

- HSE studies • Pilot plant has been modified for the production of- Agronomic trials Urea-ES- Economic studies- Technical studies

• Similar Additive and Emulsion system for ES is • UFT/Kimre have developed a set of advancedalready used by MAP and DAP fertiliser producers scrubber systems which meet all modem

requirements.• These are adaptable to Urea-ES

Thiogro <®> thyss*nkrupp

Urea-ES Fluid Bed Granulation Process

Thiogro

• Requires elemental sulphur, either as solid or liquid

• Liquid sulphur and liquid urea are immiscible due to differences in surface tension and density, and will separate quickly

• By using a high shear dispersion unit and a proprietary additive, this Shell Thiogro technology can safely1 and efficiently combine urea and sulphur into a stable emulsion containing fine particles of elemental sulphur (avg. >40 microns)

• The emulsion can be granulated in a UFT fluid bed granulation plant into Urea-ES granules

Mixing of Sulphur and Urea

A stable emulsion of urea and sulphur cannot be achieved since the two

liquids differ significantly in surface tension and density

Segregation of Urea and Sulphur

Thiogro

How to form stable emulsion?=» Additive

: Homogenization

Upon solidification, they separate quickly into an heterogeneous mixture.

Pure Urea

Pure Sulphur

thyssenkrupp

UFT Fluid Bed Urea Granulation Process - Urea

Thiogro

9Jf) f>0Q

u rea-co riuta oea ^ranujaiion rrocess Operating Principle of & ThtoMHt

A high-shear dispersion mil! uses a rotating impeller the “rotor", encased inside a fixed slotted impeller or ‘stator', typically powered by an electric motor, creating a combination of mechanical and hydraulic shear which efficiently ‘breaks' and wet-out of the sulphur phase.

1 The high-speed rotation of the rotor blades exerts a powerful suction, drawing material into the rotor/stator assembly and accelerating the particles to tip speeds up to 50 m/s

2 The combination of mechanical and hydraulic shear, generated by the turbulence and rapid changes in local flow directions within the slots produce efficient breakage and wetting-out of the immiscible non-continuous phase (sulphur)

3 Sulphur is then “microencapsulated” by the additive thereby stabilizing the emulsion within the required particle size.

4 At the same time, fresh materials are continually drawn in, maintaining the mixing and pumping cycle

5 Additional propellers, head-plates and baffles, may be added and are designed to help achieve a specific flow pattern

Thiogro m (jibtbys&enkrupp

Urea-ES Fluid Bed Granulation ProcessOperating Principle of a ThioMill

A high-shear dispersion mill uses a rotating impeller the “rotor”, encased inside a fixed slotted impeller or “stator”, typically powered by an electric motor, creating a combination of mechanical and hydraulic shear which efficiently ‘breaks’ and wet-out of the sulphur phase.

1. The high-speed rotation of the rotor blades exerts a powerful suction, drawing material into the rotor/stator assembly and accelerating the particles to tip speeds up to 50 m/s

2. The combination of mechanical and hydraulic shear, generated by the turbulence and rapid changes in local flow directions within the slots produce efficient breakage and wetting-out of the immiscible non-continuous phase (sulphur)

3. Sulphur is then “microencapsulated" by the additive thereby stabilizing the emulsion within the required particle size.

4. At the same time, fresh materials are continually drawn in, maintaining the mixing and pumping cycle.

5. Additional propellers, head-plates and baffles, may be added and are designed to help achieve a specific flow pattern

ro thyssenkrupp Uhde Fertilizer Technology

Emission Reduction Systems for Dust and NH3Urea Dust and optional Acidic Scrubbing (Kimre Internals)

Process Condensate MaKe-Uf),

41 Dust Scrubbing-*!»^

TypicalGranulator Scrubber

Make-up

Kon-Tane® Scrubbing stage

B-Qon® Demister stage

ttiyssenkrupp Uhde Fertilizer Technology

UFT Fluid Bed Urea Granulation ProcessUREA-ES Recycle Evaporation

Cooling Water

Condensor

Evaporation

UREA-ES Solution

ProcessCondensait^

from Scrubber

Cone. UREA-ES Solution

Modifications to an existing UFT fluid bed granulation plant

Modification Benefit• New Scrubbing system • Reduced pressure drop and power consumption

• Higher efficiency

Small, dedicated evaporation unit• No contamination of upstream synthesis• Increased overall evaporation capacity• No additional steam consumption

• Same plant can produce urea and Urea-ES (in• More flexibility of Bulk handling system to prevent campaigns)

cross-contamination of produces) must beimplemented. No bagging required.

• Infrastructure for Sulphur to be investigated (Supply, Handling, Feeding)

• High shear Dispersion Unit is robust and trouble- free

<®>thyssenkrupp

llhde Fertilizer Technology

UFT’s Batch Pilot PlantThe making of Urea-ES

Sulphur Sulphur(Sohd) Melter

ThK>Add -

UtmMftttor

P Urea I Addrtiva

Thiogro

_____________ If; i Htt-:._____________________________________________

Ambient Air

DispersionUnit

Dust I NH, Recovery System

Offgas

d ) №yH*nttrupp

U M t N ittte*» Ttofcnfttogy

UFT’s Batch Pilot PlantThe making of Urea-ES

Single Nozzle Granulator

Scrubber

Thiogro

Urea-ES Fluid Bed Granulation ProcessThe making of Urea-ES in UFT’s Pilot Plant Urea - ES with ~3%S

tt> vsr>aThiogro thyssenKrupp

Llhde Fertilizer Technology

22 | 02 03 20161 Nitrogen & Syngas, Beilin j Or Franzrahe, Rafael Gaicia

Sulphur distribution in Urea-ES

Thiogro

Urea-ES 43-0-0 6-7S Sulphur Particle Size ~10-20pm

Uniform dispersion of sulphur particles

thyssenkruppUhde Fertilizer Technology

11 Oe I ranzrahe. Ralsei Garcia

Nitrogen + Syngas 2016

Giuseppe Di Ruocco Process Manager

Eurotecnica

SEAMLESS INTEGRATION OF A EUROMEL* JCUMMFRLANT INTO A NITROGEN BASED FERTILIZER COMPLEX

Giuseppe Di Ruocco - Process Manager Nitrogen & Syngas Conference, March 2nd 2016

Berlin, Germany

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EUROMEL® m elam ine Off-gas Tailored Set-ups

Off-Gas 20 Off-Gas 10 Zero Water Return

no additional water at urea synthesis

Melamine

Further options for colorless start-upBypass of the absorption tower

Typical plant behaviour during start-up

Cost-effective measure with high impact

• Cold Fe-zeolite catalysts adsorb N02 (NO not present at low temperatures)

* During heating desorption occurs

Temporary storage of NOx on catalyst surface

T T --------I -----9 - - , —-r

Dynamic operation of EnviNOx®-reactor

-> Dynamic operation: Reduce N 02 with ammonia while it is still adsorbed!

Challenges for DeNOx/EnviNOx®-units during start-up and shutdown

Prevention of the formation of ammonium nitrate

ta il gas turb ine

NH3 c (gas)

tail gas (to stack)

EnviNOx*reactor

Expansion of tail gas leads to cooling of tail gas at expander

Ammonia slippage causes risk of ammonium nitrate formation at lower temperatures

Limit temperature for NH3 injection in EnviNOx®-reactor: 80°C

Temperature d/s turbine depending on temperature u/s, pressure ratio, and efficiency

Prevention of ammonium nitrate formation needed

thyssenkfupp Industrial Solutions - Product Development ( u T )18 | March 3^, 2016 | Sennce options (or colorless startup and shutdown of a nitric acid plant I Dr. Johannes Dammeier H J Ü '

Prevention of the formation of ammonium nitrate

tail gas (to stack) A P01/ bar Tt /*C T0/*C

1 140 80

3 210 80

5 260 80

7 300 80

9 330 80

11 350 80

High temperatures for high-pressure and dual pressure plants needed!

Prevention of ammonium nitrate formation needed

Prevention of the formation of ammonium nitrateInstallation of an expander bypass

tall gas (to stack)

• Adjustable bypass or extraction turbine for start-up

• Lower turbine efficiency and less cooling

• Temperature > 80®C

• Venting of turbine still required

• Higher power demand of compressor drive

• Further investigations/co-operation with turbine manufacturer necessary

»ywmuMpti mmM 8<é é w h i - Product OMtopmnl

Prevention of the formation of ammonium nitrateInstallation of an expander bypass

M) 9M (to atocfc)

Adjustable bypass or extraction turbine for start-up

Lower turbine efficiency and loss coolingTemperature > 80*C

Venting of turbine still requiredHigher power demand of compressor drive

Further investigations/co-operation with turbine manufacturer necessary

Prevention of the formation of ammonium nitrateSteam injection upstream of the expander turbine

tail gas (to stack)

Water vapour pressure above a saturated ammonium nitrate solution

Temperature [*C]

1 Oependng on gas température temperature drop, mnmonm/HO* ratio

tivjssenkrapp ïndusSnal Saluions - Product Dew tapment

tail gas (to stack)

Water vapour pressure above a saturated ammonium nitrate solution

Temperature [°CJ

tail gas (to stack)

• Water prevents deposition

• Tail gas turbine must be suitable for steam injection

• Further investigations/co-operation with turbine manufacturer necessary

Options for colorless start-upPlanned shutdown: Keep compressor in operation

tail gas(to stack) nh3

Options for colorless shutdownBlocking of the plant/EnviNOx®-Dynamics

tail gas(to stack) NH]

Options for colorless shutdownBlocking of the plant/EnviNOx<S>-Dynamics

tail gas

Blocking of the plant/EnviNOx®-Dynamics

• Blocking of plant + controlled release through EnviNOx®-Dynamics unit

No emissions till the very end

• Blocking of plant + controlled release through EnviNOx®-Dynamics unit

EnviNOx®-Dynamics

• Adapted for small flow rates

• Easy heating of these flows by electricity/steam

м т :

Options for colorless start-up and shutdown

Tail gas heating options

• Option 1 High pressure steam available

• Option 2 Fuel burner or electrical heating

Start-up Planned Shutdown Unplannedshutdown

Medium High-/dual Medium HigtWdual pressure pressure pressure pressure

Option for tail gas heating___________________(C /f_____ ( ^ f _____ __________Q f

Bypass of the absorption tower________________________ ( ^ / f

Dynamic operation/catalyst as storage for NOx & O f

Installation of an expander bypass &/... /TV/

Steam injection upstream expander Q ) / V ©/""V

Blocking of the p!ant/EnviNOx®-Dynamics Q ) <3 >

thyssentoupp Industry Solutions - Product Development25 | March 3"*, 2016 | Service options for colorless start-up and shutdown of a nitric acid plant | Or Johannes Dammeier

Summary and OutlookOptions for colorless start-up and shutdown

Tail gas heating options

• Option 1

• Option 2

High pressure steam available

Fuel burner or electrical heating

Start-up

Medium High-/dual pressure pressure

Planned Shutdown

Medium High-/dual pressure pressure

Unplannedshutdown

Option for tail gas heating O f O f O f QfBypass of the absorption tower S L ___Q LDynamic operation/catalyst as storage for NOx Of O fInstallation of an expander bypass

Steam injection upstream expander

thyssenkmpp Industrial Solutions - Product Development25 I March 3а. 2016 J Service options for colorless start-up and shutdown of a nitric acid plant | Dt. Johannes Dammeier

Summary and Outlook

• Specific case study needed for every individual plant

• Options to custom design or revamp the plants to meet emission targets

• Further development of presented measures is a priority at thyssenkrupp Industrial Solutions

• For measures regarding expander: close collaboration with manufacturer required

• Reasonable combination to ensure colorless start-up and shutdown seems feasible

thpssenknjpp tndustnal Solutions - Product DevelopmentЗв I March 3* 2016 | Senke options tor colorless start up and shutdown of a n№c acid p la it I Or W in w O— niH

Christian Goerens Manager Applied Technology

Umicore AG & Co. KG(Platinum Engineered Materials)

Who we areumicorePlatinum Engineered

Materials

A global materials technology

On© of three global leaders in emission control catalysts for fight-duty and heavy-duty vehicles and for at! fuel types

and recycling group

A leading supplier of key materials for rechargeable batteries used in portable electronics and hybrid & electric cars

The world’s leading recycler of complex waste streams containing precious and other valuable metals

uiooai presence:10,429 people, 64 manufacturing sites

umicorePlatinum Engineered

Materials

■ H F 2 March2018©*Umicore 3 aombinma MtWb&mkb 4r W W W CMtKtrlU

Strong commitment to innovation

R&D spend € 145 m

5.5% of revenues w invested in R&D

Focus on clean mobility alii and recycling

^ 539 patent families,43 patents filed in 2014

Materials

Combined Horizon 2020 clean mobility and recycling

Horizon 2020 other

Post Horizon 2020 and other

fjjjpPAC. ^ umicore

Platinum Engineered Materials

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Multi-Combination Gauze Pack

MPAC - the next generation of gauzes umicoreOriginating from a tradition of innovation Materials

invention of gauze systems

increased number of

Further development of gauze systems

Addition of system gauzes

2009 2014 i

MKSprecise

combinations

-> functionalities

*♦ designs

( MPAC

MPAC - the next generation of gauzes-> Technologies and Materials

umicorPlatinum Engine«

MATERIALS

TECHNOLOGIES

► Alloy composition

► Alloy functionality

► Purity standards

► Advanced refining

► Improved wire-drawing &

surface finishing

► Knitting software

development

► Geometry► Active Surface

► Diameter

STRUCTURES

► Knitting patterns► Gauze weight► Adjustable gauze density

MPAC - the next generation of gauzes-> Technologies and Materials

umicorë^PtaHnum Engineered

Materials

TECHNOLOGIES

► Advanced refining

► Improved wire-drawing &

surface finishing

► Knitting software

development

MATERIALS

► Alloy composition

► Alloy functionality

► Purity standards

► Geometry► Active Surface► Diameter

STRUCTURES

► Knitting patterns► Gauze weight► Adjustable gauze density

Conventional Gauze ProductionOverview of commonly used technologies

Weaving Weft knitting

► Catalyst Gauzes ► Catalyst Gauzes► Getter Gauzes► Separator Screens

Materials

Warp knitting

► Catalyst Gauzes

Images © under GNU Free Documentation License

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MPAC - Gauze Production-> Flat-bed knitting technology

Umicore’s flat bed knitting technology

Materials

Single-piece manufacturing► Production flexibility

► Tailored gauzes

► Short production lead times

► Short reaction time

► Great product variety

4 High degrees of freedom

4 Impressive number of combinations possible

9 aornbinirig competencics -f*r cxùtlknu

Single-layer catalyst gauzes PLATINIT® Various types of knitting patterns

umicore^Platinum Engineered

Materials

Single-layer gauzes for nitric acid plants► Atmospheric and low pressure plants► Medium pressure plants

► High pressure plants

Dedicated features for NA plants► Adjustable porosity / gauze structure

► Decreased PGM losses

► Very low pressure drop

Individualized gauze settings► Diameter, composition, porosity

March 2016 © Umicore10 c0mhViiVi0 MmplfcncKfe -fir frob&& zxccUtme

MPAC - the next generation of gauzes-> Case Study: Medium pressure plant

Materials

Q p a c

► Campaign Length: 330 days

► Net losses: 58 mg/tHN03

► 0 Selectivity: > 96,7 % (NO)

► Installation weight: - 3 kg

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MPAC - R&D-> Continuous development approach

Research & Development

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МРАС - R&DChemical Modelling

Computational Fluid Dynamics

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InletFlow

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Materials

ChemistrySolver,

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NH3motefraction

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tivity

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Materials

Labscale reactors

MPAC - R&D-> Data Analysis & Data Mining

Evolution. dati_u4.M20 (GPLS)Colored according to values in DS1.Vaoable(NO selectivity)

051 NO selectivity

in9.0S 9,7 9.85 99 995

XVar<NHJ contenl (%p

Materials

Evolution,data _u4.M20 (OPLS), genau wie M 10 (2ndary 10 aufge *G sdetnviiy Colored occonfng to values in DSl.VariabkKNO sek J w

XVarf NH 3 contel4%ft iu u m

March 2016 O Umicore 19 C#n4btnir10 C0WfdcnC*tt> 'jir ytKtVb cxcclknct

B Nitrogen + Syngas 2016

Daniel Gullberg Engineer

Sandvik Materials Technology

Nitrogen + Syngas 2016

Daniel Gullberg Engineer

Sandvik Materials Technology

BIMETALLIC TUBES FOR NITRIC ACID APPLICATIONSD. Gullberg, J. Wallin, M. Senatore

Bimetallic Tubes for Nitric Acid Applications

NITRIC ACID

CHARACTERISTICS

• One of the strong acids• Strongly oxidizing• Importance for fertilizer production• At low concentrations it helps forming a

protective oxide on stainless steels• Corrosive for all stainless steels at high

concentrations and/or temperatures

Bimetallic Tubes for Nitric Acid Applications March 5,2018

STAINLESS ST EELS

IN NITRIC ACID APPLICATIONS

* Low carbon austenitic stainless steels• Satisfactory for most nitric acid applications

Grade Materialtype

UNS No. Microstructure Comment

Sandvik 3R12 304L S30403 Austenitic Most common grade

Sandvik 2RE10 310L S31002 Austenitic Special grade for nitric acid

4 Bimetallic Tubes for Nitric Acid ApplicationsSANDVIK

March 3. 201« i s H H H H I

CORROSION PRO PERTIES

APPLICABILITY OF STAINLESS STEELS

« Iso-corrosion curves is a useful tool• Sandvik 3R12 is a useful material in

many nitric acid applications• Sandvik 2RE10 allows for higher

temperature and concentrations• Sandvik 2RE10 can extend the

lifetime extensively compared to 304L

HNO, concentration

ALLOY COMPOSITION

INFLUENCE ON CORROSION PROPERTIES

• Chromium is the most important alloying element- Forms a protective oxide- Passivity is more easily maintained- Lowers corrosion rate- Increases the transpassive potential

• Carbon will promote carbides during sensitization• Impurity elements such as P and S are negative

due to formation of segregations

i------ 10---- 25----- 30-----35----- 55----- 85----- 70------*Tim«, minutes

C, S, and P reduction in the AOD

e Bimetallic Tubes for Nitric Acid Applications

[SANDVfiClMarch S,2016

PRESEN CE OF CONDENSATESPARTICULARLY CORROSIVE

• Much more corrosive than the liquid bulk• Can cause transpassive corrosion• Large surface to solution volume ratio• Slow renewal and accumulation of

reaction products• Fast increase in corrosion potential

OuO< 1.1

o° 0.9IE-06 IE-05 IE-04 IE-03 IE-02

Current density, Log( | i | ), A/cm2

304L in 65% HN03 at room temperature

SANDVt!Bimetallic Tubes for Nitric Acid Applications March 3.2016

PROBLEM AREAS

• Where the highest temperatures are found

• Typically where condensation takes place

• Classic problem for cooler/condenser

• An advanced stainless steel can extend the life time

0 First condensate formed - 120-130‘C

SoN Reboiling • corrosion increases with Increasing gas inlet temperature

BIMETALLIC TUBESTAINLESS STEEL TUBE WITH ZIRCONIUM LINING

• Sandvik 2RE10 - Pressure bearing part- High alloyed specialized stainless steel

• Sandvik Zr 702 - Corrosion protection- Exceptional corrosion resistance

• Bonded by mechanical bonding

10 Bimetallic Tubes for Nitric Acid Applications

BIMETALLIC TUBESTAINLESS STEEL TUBE WITH ZIRCONIUM LINING

• Sandvik 2RE10 - Pressure bearing part- High alloyed specialized stainless steel

• Sandvik Zr 702 - Corrosion protection- Exceptional corrosion resistance

• Bonded by mechanical bonding

PRODUCT SPECIFICATIONS

• The zirconium tube is produced according to ASTM B523- Thickness 0.7 mm

• The outer component meet the requirements of ASTM A213 and ASME Code Case 2591

Chemical composition (nominal) weight%.Zr+Hf Hf Fe+Cr H N С О

Sandvik Zr 702 >99.2 <4.5 <0.2 <0.005 <0.025 <0.05 >0.16С Si Mn P S Cr Ni Mo

Sandvik 2RE10 <0.015 £0.15 1.8 £0.020 <0.005 24.5 20 <0.10

ic Tubes tar Nitric Acid ApplicationsISANDVKI

гоїв вИНННВ

USE IN NITRIC ACID PLANTSTYPICAL APPLICATION; COOLER/CONDENSER

Zirconium inner tubeTube sheetNo corrosion

Bimetallic Tubes for Nitric Acid Applications March 3,2018SANDN

HEAT TRANSFER PRO PERTIES

• Important property for HX tubes• Normally measured on flat samples• Not measured on the bimetallic tube• Modeling was used instead

Thermal conductivity, W/mK

Temp, °C 2RE10 Zr 702

20 13 22100 15200 17300 19

SANDVIKSMarch 3,2016

MODEL SET-UP

• 2D-geometry• Tube dimension; 19.05x2.3 mm• Zr 702 thickness; 0.7 mm• Temperature inner surface; 100°C• Temperature outer surface; 50°C• Number of gaps and gap size varied

- Gives total contact

IS Bimetallic Tubes for Nitric Acid ApplicationsSANDVlKi

March 3. 2016

I * 18 gap« Щ Щ іІі 51* Gap height, 5 pm* Gap length 1971 pm* Total contact; 22%

RESULTS FROM MODELING

£ 12 ♦ ♦C/3 ♦C CO b 8

• | ♦ Large gaps, 2 mmф 4 e Small gaps, 60 ц т>

- - Perfect contactфШ 0

0% 20% 40% 60% 80% 100%

Contact percentage

17 Bimetallic Tubes far Nitric Acid Applications March 3,2016

CONCLUSIONS FROM THE MODELING

• Heat transfer is good even with small bond gaps• Gap size is more important than the total contact• The gap height has no large impact• Credible results

- Similar tubes are used as stripper tubes in urea plants

TUBE TO TUBE SHEET

Safest option is to remove zirconium from the tube end

SPECIAL CONSIDERATIONS WHEN WORKING WITH BIMETALLIC TUBES

• Weld should only involve the outer component

• Expansion and welding can potentially damage the mechanical bond

• Melting of zirconium needs to be avoided

Bimetallic Tubes for NitricSANPVi»

March 3,2016

MOCK-UP FABRICATION

MATERIAL

• Tubes. Sandvlk 2Rf 10/Zr 702 with dimension 19 05x2 11 mm- Zirconium thickness; 0.7 mm

• Tube sheet. AISI type 304L with thickness 50 mm• Welding consumable; 0.8 mm AISI type 310L welding wire

- Seal welding with 2 passes ~ Shielding gas. argon

VARIATION OF PARAMETERS

EVALUATION OF REMOVAL DISTANCE AND EXPANSION RATE

Removal distance;- 5 mm - 8 mm -1 0 mm -2 0 mm

Expansion rate (expansion by rolling);- No expansion- Mild expansion (<2%)- Expansion (3-5%)

Û:< e x P- >

Bimetallic Tubes far Nitric Acid Applications

REMOVAL DISTANCE

AVOIDING MELTING AND HEAT-TINT

• 5 mm; heat-tint reaches the zirconium• 8 mm; almost reaches zirconium• £10 mm; safe distance

This type of seal-weld would not have been possible without removing the zirconium from the tube end.

SANDVIKBimetallic Tubes for Nitric Acid Applications

BOND EXAMINATIONCHECKING DISBONDING FROM HEAT OR EXPANSION

• Not possible to measure the bond strength

• Disbonding was examined by optical microscopy

• Interface closest to the weld• In the expansion zone

Bimetaffic Tubes far Nitric Acid Applications March 3, 2016

BOND EXAMINATIONINTERFACE; 5 MM REMOVAL

EXPANSION ZONE; 3-5% EXPANSION

BOND EXAMINATION

INTERFACE; 5 MM REMOVAL EXPANSION ZONE; 3-5% EXPANSION

MODIFIED HUEY TEST

• Boiling 65% HN03• 5x48 h• Cut surfaces polished with 600 grit paper• Evaluation by examination• Corrosion rate was not calculated

CORROSION TESTING

CORROSION TEST RESULTS• Most corrosion on the 304L tube sheet• No severe corrosion of the weld metal, HAZ,

or bond zone• The tube inlet showed discoloration but no

severe corrosion• Zirconium unaffected• No attack on the interface between 2RE10

and Zr 702

TUBE PRODUCTION AND TESTING

Bimetallic Tubas for Nitric Acid Applications March 3, 2016

TUBES FOR THE FIRST TEST INSTALLATIONSMALL HEAT EXCHANGER IN A NITRIC ACID PLANT

Sandvik 2RE10/Zr 702Tube dimension; 19.05x2.3 mmThe performance of the heat exchanger will be presented in future papers

> • • • • • • • • • • • • • • • • • • •w m w M M t » '» • • • • • •<

• • • • • •----------9 » » mm + e,e ;e;e f«|ew■PI»:*.«« • • •• • • •W M M IW S W :* '» • • •

• • • • • • • •• • • • • • • • 9Lml0»m

• • • • • • • • • • • • • • • • • • • •

SANDVIK!

MECHANICAL AND CORROSION TESTINGHuey (ASTM A262 pr. C) testing of the outer component

- 0.067 and 0.065 mm/year Mechanical testing according to ASTM A213

Lot Yield strength, Tensile Elongation, % Hardness,MPa strength, MPa HRB

1s* lot 394 585 38 8 8 1 2nd lot 410* 590* 36* 88‘Average value from two or more tests.

MEASUREMENT OF THE MECHANICAL BOND

Measured on 20 samples from several tubes Average spring back; 70 pm, all above 60 pm Close to the maximum attainable bond

Bimetallic Tubes for Nitric Acid ApplicationsjSAfjjgVjKj

Sandvik 2RE10/Zr 702 bimetallic tubes for nitric acid applicationsWelding trials have been performed

- Maintained bond- No weak spot at the interface between

2RE10 and Zr702Good heat transfer

SANBVHCMarch 3,2018 H H H H H

7rirl 9©n + syngas 2016 -...

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