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HeraeusNitro Technologies
W. C. Heraeus
2
Locations
Heraeus Nitro Technologies is a business unit of W C. Heraeus, the largest company in the HeraeusGroup. Heraeus Nitro Technologies is deeply rooted in the history of the company as well as in today’soperations.
It draws heavily on the expertise,manufacturing and research resources, logistics and management competence of the whole group.Manufacturing facilities are located in Europe, the United States, CentralAsia and the Far East with sales offices in all major markets.
Heraeus Nitro Technologies focusesits activities on providing productsand services for industrial ammoniaoxidation and hydrogen cyanide production. Groundbreaking inno-vations, technical and commercialcompetence, continuous improvementand the use of the most efficient production techniques make HeraeusNitro Technologies the worldwidetechnology and cost leader in its business area.
Heraeus Nitro Technologies Locations
W.C. Heraeus GmbH – HeadquartersHanau /Germany
Heraeus Materials Technology Shanghai Ltd., P. R. China
Ravindra Heraeus Private Ltd., IndiaHeraeus Metal Processing Inc., USA
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GauzesCatalyst Gauzes
Catalyst gauzes for the oxidation of ammonia to nitrogen oxide
By courtesy of Krupp Uhde, Dortmund, Germany
By courtesy of Krupp Uhde, Dortmund, Germany
Heraeus Nitro Technologies looksback on decades of experience incatalyst gauze manufacture. This longterm experience and the focus on thescience of precious metals ensuresthat the materials used for the manu-facture of catalyst gauzes fulfil themost stringent standards in respect to their quality and purity. Over yearsof close monitoring of gauze perfor-mance, specific elements and sub-stances which adversely influence either the catalytic activity or mecha-nical stability of the gauzes have beenidentified. Based on this experience,dedicated procedures have been put in place at Heraeus Nitro Techno-logies which guarantee an excellentperformance of the gauzes.
Heraeus Nitro Technologies not onlysupplies catalyst gauzes but alsoadvises customers on the best cata-lyst configuration, alloy and structure.Using computer programs, optimizedcatalyst systems can be proposed to suit individual process parameters:
Heraeus Nitro Technologies main-tains a dedicated and segregatedstock of material for catalyst gauzemanufacture
The most modern material analysistechniques are used to control thematerial composition and level ofimpurities
All substances and compoundswith potentially negative influenceon catalytic activity are eliminatedfrom the manufacturing process
All gauzes are activated by a dedicated procedure in order to ensure immediate light-off and rapid surface restructuring
More than a decade ago, Heraeusfirst developed and introduced a newproduction technique for catalyst gauzes: warp knitting. This patentedproduction technique proved so successful that soon the majority ofcatalyst gauzes in use throughout theworld are now manufactured usingthis technique. The traditional wovencatalyst gauzes have almost entirelybeen replaced by knitted products.
The choice of the warp knitting tech-nique was made by Heraeus afterextensive comparative testing of several different gauze structures produced with varying productiontechniques supported by mathema-tical modelling and simulation of thereaction processes. The warp knittedgauze proved best due to its out-standing performance under industrialoperating conditions and because of the versatility of the warp knittingproduction technique itself.
The Heraeus Nitro Technologies warpknitted catalyst gauzes are uniquely well suited for catalyst reactions due
to their inherent features:high mechanical strength and form stability“self repairing” behaviourlow pressure drophigh surface arealow platinum lossesminimal rate of rhodium oxide formationhigh conversion rate and selectivitylong operating cycles
The versatility of the warp knittingtechnique enables the manufacture of gauzes with:
a large selection of gauze structuresa large selection of specific catalyst weightsa wide range of gauze diametersa wide range of wire diametersa multitude of alloy specificationsfast production and short delivery times
Heraeus Nitro Technologies continuesto offer woven products for the fewremaining customers wishing to usethis technology.
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KnittingWarp Knitting
Warp knitted structure
Heraeus Nitro Technologies has succeeded in developing a catalystsystem, FTCplus, which reduces the nitrous oxide emission at source.
FTCplus has been commercially available since 2000. After installa-tion, the emissions of nitrous oxidehave been reduced on average by more than 30% over extendedcampaign lengths in many industrialapplications. FTC and FTCplusconsist of a number of metallic gauzelayers and can be installed in virtuallyany reactor. No changes to the reactoritself and no additional catalyst isrequired in order to operate FTCplus.
Both FTC and FTCplus catalystsystems can be delivered in the formof individual gauze layers or pads ormounted on a stretcher.
Detailed documentation and installa-tion information as well as on-siteinstallation support are available.
FTC, Functional Total Control, is acompletely new concept for the cata-lytic oxidation of ammonia which hasbeen available since 1996 solely fromHeraeus Nitro Technologies.
Using computer models, a fully inte-grated catalytic package is designedspecifically for each reactor. FTC isdesigned to reduce total productioncosts: the cost savings are primarilyachieved by reducing precious metallosses and reducing the precious metalweight of the installed catalyst. FTCdoes away with the requirement ofcatchment systems to be installed inthe reactor.
To accomplish this, FTC systems utilise specially developed, complexalloys which enable the total weight of precious metals required to be sub-stantially reduced. When comparedto conventional catalyst systems, costreductions of up to 35% per tonne of nitric acid produced have beenachieved in numerous industrial appli-cations. This result has been achievedwithout sacrificing ammonia conversionefficiency or campaign length.
On the contrary, ammonia conversionefficiencies are bench marked overeven extended campaigns. FTC is suitable for virtually all reactor types.
FTC and FTCplusFTC and FTCplus
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1916:woven gauzes
Pd Wire: Active Pt is absorbed and diffuses to wire core
FTC Wire: Active Pt is absorbed and remains on wire surface
1966:woven gauzes+catchment gauzes
1992:warp knitted gauzes + catchment pack
1996:FTC Systems
2000:FTCplus Systems
FTCplus
2003:FTC-HR
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N2O Abatement Catalyst HR-SC
Secundary CatalystsSecondary Catalysts
The greenhouse gas N2O is known to have a global warming potential310 times higher than CO2. Annually,about 1.2 mio. tonnes of this gas areemitted by the nitric acid industry,which is equivalent to the CO2
emissions of 80 mio. passenger cars.
On one hand, the national environ-mental legislation has become tighterin some countries after commencementof the Kyoto Protocol. On the otherhand, the Kyoto mechanisms allowthe industry to implement emissionreduction projects (CDM/JI) generatingcarbon credits. Industries emitting hugequantities of CO2 to the atmosphereand plants where emission reductionsare only viable with very high invest-ment have a definite demand for carbon credits.
Heraeus has developed a N2O abate-ment system (HR-SC) for nitric acidplants which enables the reduction ofemissions to any desired level.
The catalyst consists of materialscommonly used in NH3 oxidationreactors. This ensures that no newmaterials are present endangering the product. The HR-SC system is made of precious metal coatedceramic pellets which are filled into steel cassettes designed to fit into the reactor.
Depending on operating conditionsand the required level of emissionreduction the catalyst layer thicknessin medium pressure plants is typicallybetween 20–60 mm causing an addi-tional pressure drop of 1 to 40 mbar.The Heraeus N2O reduction catalysthas been subjected to an intensivedevelopment program in small scalereactors as well as in commercialinstallations with an output of morethan 1,000 tonnes of acid per day.
Heraeus is marketing the HR-SCsystem on a lease basis, charging the customer monthly based on thequantity of acid produced (in tonnesof HNO3 100 %). This business model has major advantages:
Cost transparency for the customer
Technical support and trouble shooting are included in the lease fee
Free of charge disposal of the spent catalyst at the Heraeus site
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Secundary CatalystsSecondary Catalysts
Installation Modus of the N2O Abatement Catalyst
Single segment of secondary catalyst
Preparation of reactor
Completed installation
Installation by our experts
The HR-SC is mounted directly beneath the primary catalyst (gauzes).In most cases, there are no modifica-tions to be made prior to the installationof the Heraeus Secondary Catalyst.
On rare occasions, the basket has tobe reinforced or a steel support gridhas to be lowered in order to createenough space for the system. Normally,some Raschig rings equivalent to thecatalyst layer will be removed.
Chronology of HR-SC installation:
1. Catalyst segments are delivered tothe customer packed in a woodenbox (usually one per reactor).
2. The wooden box is lifted onto the platform in the proximity of the reactor.
3. Heraeus will dispatch an applicationengineer, who will be present duringthe installation for assistance.Installation of the first HR-SC willbe carried out by Heraeus engineers.
4. Part of the Raschig rings need tobe removed: the layer of Raschigrings depends on the thickness of the catalyst package.
5. Raschig rings have to be levelledover the entire reactor area.
6. A fine mesh Kanthal screen isinstalled in the reactor to protectthe surface of the Raschig rings.
7. An alumina gasket is installed at the edge of the basket.
8. The steel cassettes are installed in the reactor individually. Eachsegment is tagged, so it can be identified in the installationsketch provided by Heraeus.
9. The segments are connected using a special tool.
10. After having installed the HR-SC system, the reactor can be fitted with the catalyst gauzes.
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N2O abatement catalyst can beinstalled without major reactormodifications – no necessity forreactor redesign
The HR-SC system can achieveover 90 % reduction in N2O emissions and thus earns largenumbers of carbon credits
High thermal stability
No mechanical abrasion of the preforms
No leaching of the catalyst layer
The system does not contain any potentially hazardous materials
There is no measurable effect on the oxidation efficiency
Catalyst stability has been provenover many months in industrialreactors
Low pressure drop
Cost optimization by combinationof FTCplus-gauze systems and HR-SC
HR-SC – Summary of Advantages
800
600
400
200
0
0
FTCplus
N2O
in t
ail g
as [
ppm
v]
Catalyst layer thickness [mm]
N2O
in t
ail g
as [
ppm
v]
Standard HR-SC
10 20 30 40 50
Typical medium pressure plant
1200
800
400
0
Gauzes + 20 mm catalyst layer packGauzes only
Secundary CatalystsSecondary Catalysts
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Corrugation Technology
Heraeus offers a number of innovativesolutions based on the corrugatedtechnology. Corrugation was originallydeveloped for use in high pressurenitric acid plants in order to allow theinstallation of catchment or gettergauze technology while avoiding theproblems of massive pressure dropoccurring in the reactor. Heraeus hasfurther developed this basis techno-logy to extend its utilization into thefield of catalysis as well as modifyingit for application to packaged catalystsolutions.
A major leap forward is the Heraeusdevelopment of corrugation and profi-ling technology for medium pressureapplications.
By utilizing the Heraeus MP profilingtechniques, we can achieve the following advantages for operators of reactors with diameters of 2 to 7 metres:
20 – 30 % reduction in specificload of N per unit areareduced volatilization of PGMsduring the production cycle considerably extended campaigndurationshigher ammonia conversion efficiency easy installation and removal
Each system is individually computerdesigned for the reactor, the produc-tion parameters and the specific campaign. Please ask our engineers!
Corrugated GauzesCorrugated Gauzes and Profiled Packs
Higher surface area
Longer lifetime
Higher gas throughput
Gauzes
Carriermaterial
Corrugated structure
Corrugated structure
1010
A revolutionary catalytic product whichwill eventually replace conventionalgauze products is the high technologyWafer development by Heraeus.
Wafer is a highly robust, infinitelycustomisable catalyst package forammonia oxidation which is wire-free!The CAD structures available with this technology and the flexible com-bination of varied materials integratedinto the design allow plant managersto specify the ideal catalyst for eachcampaign. Wafer offers the following
advantages over conventionalcatalysts:
Much higher porosity, leading to faster reactionsand lower propensity forside and back reactions.Lower energy requirement.
Greater active surface area, allowinghigher catalyst loading and reducingdirect precious metal installed andindirect precious metal inventories.
Built-in catalytic activation, non-geometric random forming processesresult in higher catalytic activity priorto ignition. Activity remains higherover extended periods.
Robust and damage resistant package, through integrated functio-nality a one or two piece solution isavailable for almost any application.The one or two piece solution alsoallows easy and quick installationand removal.
Can be supplied in corrugated and profiled forms, suitable for allatmospheric, medium and highpressure reactors. Please consultour engineers for your customizedsolutions.
Wafer CatalystsWafer Catalysts
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Stretcher – the upper strip and board can be removed and the catalyst opened out to lie flat on the burner
Delivery and RecyclingGauze Delivery and Recycling
Heraeus Nitro Technologies strives tomake gauze deliveries in a way whichis most convenient to its customers.Detailed documentation, installationguidelines, on-time delivery and on-siteinstallation support are all included inthe service.
Gauzes can be supplied as individualsheets, as pads or using dedicatedpacking systems.
A speciality of Heraeus Nitro Techno-logies is the delivery of gauzes on theso-called Stretcher. The Stretcher isnot only a transport but also a gauzeinstallation system. The Stretcher isplaced over the reactor and the gauzesare released in such a way that thegauze pack is installed in one quick andeasy operation into the reactor. It isextremely well suited for reactors withdiameters of 2 m and above.
Stretcher
An inherent feature of the ammoniaoxidation process is that the catalystgauzes lose weight. Platinum is lostprimarily in the form of volatile platinumoxide and to a lesser extent as particles due to mechanical losses.
Rhodium is lost in the form of rhodiumoxide which is not volatile and the losses are primarily of a mechanicalnature. The rate of total losses makeup a linear function of the logarithm ofthe daily production rate per surfacearea of the reactor: this means thatthe higher the production rate per unitarea of reactor the higher is the rateof material losses.
In today’s modern plant managementthe material lost from the catalyst cannot be regarded as material which is “lost forever”. Heraeus Nitro Technologies provides several wellestablished methods to recover nearly ninety per cent of the precious metalprimarily lost from the gauzes.
Precious Metals Recovery
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Platinum Recovery FiltersPlatinum Recovery Filters and Plant Cleaning
Platinum recovery filters are air phase particulate filters which arepositioned downstream of the plant’sheat recovery train where gas tempe-ratures are well below 400° C.
The filters not only collect particleswhich are transported by the reactiongases but also facilitate the conden-sation of the volatile platinum oxide
from the gaseous phase. The filterscan be employed with or without acatchment system.
Heraeus Nitro Technologies offers:Supply and re-packing of Platinum Recovery FiltersRefining of spent filtersRecovery rates between 30 – 50 %Low pressure drop
Platinum Recovery Filters
In modern plants substantial amounts of precious metal catalyst are retainedin the heat recovery train and largequantities of precious metals can berecovered from spent heat exchan-gers. Also, there are various non-destructive cleaning methods whichenable the recovery of preciousmetals during normal plant turnaroundsor stoppages, while also improvingheat transfer and plant throughput.
Heraeus Nitro Technologies throughour sub-contractor, 3D RecoveryEurope Ltd, provides:
Non-destructive cleaning of plantsNon-destructive and destructivecleaning of plant componentsRecovery of precious metals fromcleaning residues, PGM containingdeposits and spent filtersIncreased plant performace
Plant CleaningTubes before plant cleaning
Tubes after plant cleaning
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Technical ServicesTechnical Services offered by Heraeus
Heraeus Nitro Technologies routinelyuses a wide range of powerful investi-gation techniques for product develop-ment and customer support. The mostcommonly used technique is ScanningElectron Microscopy (SEM) in con-junction with Energy Dispersive X-RayAnalysis (EDXA).
With these methods the morphologyof the catalyst and the composition ofsurface contaminants can be quicklyand reliably investigated on small scalesamples. In more demanding situationsother techniques such as Auger Electron Spectrometry (AES) andSecondary Ion Mass Spectroscopy(SIMS) can be used for surfaceanalysis and sub-surface profiling.
These methods are further supplemen-ted by bulk material analysis techniquessuch as X-Ray Fluorescence Analysis(XRFA), Directly and Inductively Coupled Plasma Optical EmissionSpectrometry (DCP and ICP-OES).
With these modern investigationmethods Heraeus Nitro Technologiesconducts customer related studies onthe optimization of process parametersand on possible causes of operationaldisruptions. Catalytic poisons, carbonlayers or rhodium oxide deposits,which have been caused by anomaliesin temperature, pressure or gas composition during service, as well as bulk material contamination can be indentified quickly and thus beavoided in future operation.
Investigation Service
Scanning Auger spectometer
Developed catalyst structure
Rhodium oxide needles
Massive Rh203 formation
Massive Fe contamination
Mechanical damage (steam leak)
Heraeus Nitro Technologies provides atrouble shooting service to customersin relation to the use of its productsand services.
This service includes consultations by phone or on-site and is aimed atsolving any problem which may occur.
Trouble Shooting
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Technical ServicesTechnical Services offered by Heraeus
The conversion rate of ammonia intonitric oxide is the decisive cost factorin the production of nitric oxide.
Heraeus Nitro Technologies providesan ammonia conversion efficiency
measurement service which enablesthe ammonia conversion rate to beprecisely determined for an individualreactor. The service includes consul-tations, on-site measurements andtraining of employees.
Ammonia Conversion Efficiency Measurement
100
90
80
70
60
9693
2800 150 22575 300
Operating time days
NO
yie
ld
%
SEM /EDXA X-ray fluorescence analysis Optical investigation
As part of its comprehensive preciousmetals service Heraeus Nitro Techno-logies offers not only the physical precious metal cycle i. e. manufacture,processing, refining and engineering,but also a comprehensive preciousmetal management service.
The service includes:24 hour world-wide trading andacquisition of precious metalsPrecious metal leasing
Precious metal handling via customer metal accountsLocal and qualitative precious metalswapping
In addition, the customers of HeraeusNitro Technologies have a direct link to the specialists of the Heraeus Metal Trading Company who provide competent expert information andadvice on the global precious metalmarkets.
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Precious Metals ManagementPrecious Metals Management
W. C. Heraeus GmbH Engineered Materials DivisionBusiness Unit Precious Metals TechnologyHeraeusstr. 12 – 1463450 Hanau, GermanyPhone + 49 (61 81) 35 51 04Fax + 49 (61 81) 35 35 33E-mail: [email protected]/precious-metals-technology
The data given here are correct for April 2006. We reserve the right to maketechnical alterations as necessary.
Layout: 5TC, FriedbergPrinted in Germany 3M 04.2006/N Reu
USA
Heraeus Metal Processing, Inc.15524 Carmenita RoadSanta Fe Springs, CA 90760, USAPhone +1 (562) 921 74 64Fax +1 (562) 921 53 33E-mail: [email protected]: customerservice@
heraeusca.comwww.heraeusca.com
Worldwide Production Locations
China
Heraeus Materials TechnologyShanghai Ltd.1 Guang Zhong RoadZhuanqiao Town, Minhang DistrictShanghai 201108, P. R. ChinaPhone +86 (021) 64 42 62 66Fax +86 (021) 64 89 00 22E-mail: [email protected]
India
Ravindra Heraeus Private Ltd.A – 196 (A), ´F ` Road Mewar Industrial Area, Madri, Udaipur 313 003, IndiaPhone +91 (294) 249 - 00 29, -20 27Fax +91 (294) 249 - 21 77, -18 25E-mail: [email protected]