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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
Steam
BFW
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
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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
Uhde Fertilizer Technology
thyssenkrupp Uhde Fertilizer Technology
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
thyssenkrupp Uhde Fertilizer Technology
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
L a
f'
Upon solidification, they separate quickly into an heterogeneous mixture.
w M
Pure Urea
Pure Sulphur
thyssenkrupp
UFT Fluid Bed Urea Granulation Process - Urea
Thiogro
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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
Uhde Fertilizer Technology
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-*!»^
ro
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
Steam
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-:._____________________________________________
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DispersionUnit
Dust I NH, Recovery System
Offgas
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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
Typical plant behaviour during start-up
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!
Typical plant behaviour during start-up
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
A
Z f
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)
i>
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
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 [°CJ
Prevention of the formation of ammonium nitrateSteam injection upstream of the expander turbine
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 the plant/EnviNOx®-Dynamics
• 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
Blocking of the plant/EnviNOx®-Dynamics
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
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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
umicorePlatinum Engineered
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Combined Horizon 2020 clean mobility and recycling
Horizon 2020 other
Post Horizon 2020 and other
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Multi-Combination Gauze Pack
MPAC - the next generation of gauzes umicoreOriginating from a tradition of innovation Materials
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MPAC - the next generation of gauzes-> Technologies and Materials
umicorPlatinum Engine«
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► Alloy composition
► Alloy functionality
► Purity standards
► Advanced refining
► Improved wire-drawing &
surface finishing
► Knitting software
development
WIRES
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► Diameter
STRUCTURES
► Knitting patterns► Gauze weight► Adjustable gauze density
MPAC - the next generation of gauzes-> Technologies and Materials
umicorë^PtaHnum Engineered
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TECHNOLOGIES
► Advanced refining
► Improved wire-drawing &
surface finishing
► Knitting software
development
MATERIALS
► Alloy composition
► Alloy functionality
► Purity standards
WIRES
► 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
umicorePlatinum Engineered
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Warp knitting
► Catalyst Gauzes
Images © under GNU Free Documentation License
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Umicore’s flat bed knitting technology
umicorePlatinum Engineered
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
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Single-layer catalyst gauzes PLATINIT® Various types of knitting patterns
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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
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► Net losses: 58 mg/tHN03
► 0 Selectivity: > 96,7 % (NO)
► Installation weight: - 3 kg
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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
Bimetallic Tubes for Nitric Acid Applications
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
ppm
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
1.2
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
lANDN
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
10 Bimetallic Tubes for Nitric Acid Applications
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
KEY
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
14 Bimetallic Tubes for Nitric Acid Applications
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
20
E 16
£ 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
Bimetallic Tubes for Nitric Acid Applications
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
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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
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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
Wmmmm
( E
Bimetallic Tubes for Nitric Acid Applications
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
27 Bimetallic Tubes for Nitric Acid Applications
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
o°
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
Bimetallic Tubes for Nitric Acid Applications
SANBVHCMarch 3,2018 H H H H H
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