tbls+ general presentation–apr. 2008/ik cert.-no.: de ...general presentation-apr2008-ik.pdfpenox...

PENOX GmbHTBLS+® General Presentation–APR. 2008/IK Cert.-No.: DE 7000104

TBLS+®

General Presentation

by PENOX GmbH, Cologne

TBLS+TBLS+®®

General PresentationGeneral Presentation

by PENOX GmbH, Cologneby PENOX GmbH, Cologne


LocationsLocations

••

* Joint ventures

** **


Group StructureGroup Structure

MgmtGroup

0.9%

Penox Penox GmbH GmbH Cologne, Germany

Penox Penox ItaliaItalia S.r.lS.r.l. La Spezia, Italy

Penox Penox SASA

Senlis, France

100 %100 %

NOVA CapitalLondon

49.9%29.4 %

Lindgens & SöCologne

HeubachSalzburg

19.8%

PENOX ENGINEERINGPENOX ENGINEERINGAll Sites

Penox Penox GmbHGmbHOhrdruf, Thuringia

20%20%

DUROXDUROXRio Claro, Brazil

60%60%METAL OXIDE SAMETAL OXIDE SABarcelona, Spain

COPLOSA SA COPLOSA SA Barcelona, Spain

Penox MexicoPenox MexicoMonterrey


OrganisationOrganisation

EXECUTIVE BOARDEXECUTIVE BOARDCEO CEO -- Denis Denis DoiseauDoiseau, CFO , CFO –– Françoise Françoise PetrelPetrel

SUPERVISORY BOARDSUPERVISORY BOARDR. R. LambourneLambourne (Chairman)(Chairman)

C. C. GraeffGraeff, R. , R. HeubachHeubach, M. Kelly , M. Kelly

CTOCTOF. F. Heras Heras

CSCSK. K. Sommerladt Sommerladt

COPLOSACOPLOSABarcelonaBarcelonaF. F. HerasHeras

PENOX PENOX GmbHGmbHCologne / Cologne / OhrdrufOhrdrufH.W. H.W. ZachlehnerZachlehner

PENOX PENOX ItaliaItaliaLa La Spezia Spezia

R. R. PassarottoPassarotto

PENOX MexicoPENOX MexicoMonterrey Monterrey

Dr. GonzalesDr. Gonzales

Metal Oxide Metal Oxide BarcelonaBarcelona

F. F. HerasHeras / J. Loriot/ J. Loriot

RepRep..B. B. BaillonBaillon

SecrSecr. . M. DuboisM. Dubois

DUROX DUROX Rio Rio ClaroClaro, SP, SP

P. P. StensStens


PENOX EngineeringPENOX Engineering

FRANCEFRANCE

D. Baumann

SPAINSPAIN

M. Portella

ITALYITALYR. Passarotto

G. Varella

MEXICOMEXICOE. Rodriguez

A. de la O

ENG.+ GROUP ENG.+ GROUP ProjectsProjectsHead of Engineering TeamHead of Engineering Team

R. R. Toedtmann Toedtmann Penox BartonPenox BartonHRBHRB--140/180 140/180

MetalindustrieMetalindustrieP20 ReactorP20 Reactor

Red Lead Furnaces Red Lead Furnaces SA3 and ME2SA3 and ME2

& & Related ProductsRelated Products

GERMANYGERMANY

H.W. Zachlehner


Worldwide InstallationsWorldwide Installations

~100~100InstallationsInstallations WorldwideWorldwide

Europe Europe >50>50AsiaAsia >15>15Americas Americas >10>10Africa Africa 11RussiaRussia/China 3/China 3


PENOX GmbH LocationsPENOX GmbH Locations

PENOX GmbHPENOX GmbHCologneCologne

PENOX GmbHPENOX GmbHOhrdruf SiteOhrdruf Site

PENOX S.A.PENOX S.A.SenlisSenlis -- HeadquarterHeadquarter


View of Cologne SiteView of Cologne Site


Plant Layout ColognePlant Layout Cologne

SALTPROD.

Pb STORAGEWORKSHOPS

Hafenstrasse

Deutz-Mülheimer-Strasse

Auenweg

Offices

RHEIN / HAFEN

PRODUCTSTORAGE

NOT TO SCALE


Oxide ProductionOxide Production

REDLEAD

LITHARGE

LOX

RAWOXIDE

BATTERYOXIDE

Packingfor RL & Li

DR

Mill

Mill

SODIUM ANTIMONATE

LE2LE2LE2LE2


Sulphate ProductionSulphate Production

DRYER

StoragePacking

PRECIPITATIONTANKS

ACIDS

WATER

SILO

SILO

HLSHLSHLS

LITHARGE

Centrifuge

Beltdryer

Mill

Lead Sulphatex PbO . PbSO4 . H2O

x = 0,5 - 3 - 4

+ Water+ Acetic acid+ Sulphuric acid

TBLS+ PlantTBLS+ Plant

Demin. water

station

Steam

generator


Applied Technologies CologneApplied Technologies Cologne

•• BARTON BARTON Reactor Reactor ((Battery Battery Oxide, Oxide, Litharge Litharge L5,L5, RawRaw Oxides)Oxides)

•• HEUBACH Mills (HEUBACH Mills (Battery Battery Oxide)Oxide)

•• Mixer Mixer for for OxidesOxides

•• Raking Furnaces Raking Furnaces (Red (Red LeadLead -- Batch ProcessBatch Process))

•• LE 2 LE 2 Furnaces Furnaces ((LithargeLitharge –– ContCont. . ProcessProcess))

•• Calcining FurnacesCalcining Furnaces ((Litharge Litharge L9, L9, SodiumSodium Antimonate Antimonate –– BatchBatch Pr.)Pr.)

•• Double Double Reactor Reactor ((Litharge Litharge L15 L15 for Lead Sulphate Productionfor Lead Sulphate Production))

•• High High Temperature Furnace Temperature Furnace ((molten Litharge for molten Litharge for Granulate)Granulate)

•• Lead Sulphate Wet Lead Sulphate Wet Plant (TBLS, TTBLS)Plant (TBLS, TTBLS)

•• Lead Sulphate Mill Lead Sulphate Mill Plant (TBLS+Plant (TBLS+®®))

•• Several MillingSeveral Milling and and Sifting Sifting EquipmentEquipment

•• ScreensScreens


View of View of Ohrdruf Ohrdruf Site (Site (ThurThur.).)


Plant Layout Plant Layout OhrdrufOhrdruf

22/ Granulate22/ GranulateStorageStorage

14/ 14/ TrafoTrafo

2/ 2/ LeadLead StorageStorageTruck Truck LoadingLoading StationStation

20/ 20/ ProcessProcess WaterWaterFilter + Filter + RecircRecirc PumpsPumps

B1B1

B2B2

B3B3

B4B4

Gran.Gran.

Gran.Gran.

NO

II 9

0.4

Plan

tN

O II

90.

4 Pl

ant

Silo

Storage Storage Area forArea for

GranulateGranulateandand

Battery Battery OxideOxide

Silo

Silo

Silo

Packing

area

Battery Oxide

Litharge and granulated Litharge


Applied Technologies Applied Technologies OhrdrufOhrdruf

•• BARTON BARTON Reactor Reactor ((LithargeLitharge RawRaw Oxide)Oxide)

•• BARTON BARTON Reactor with coarseReactor with coarse material material recycling recycling ((Battery Battery Oxide)Oxide)

•• Electrical heated Screw Furnaces Electrical heated Screw Furnaces ((LithargeLitharge))

•• Compactor Compactor Equipment (Equipment (Litharge Litharge Press Granulate)Press Granulate)

•• Granulate Granulate ClassifierClassifier

•• Several MillingSeveral Milling EquipmentEquipment

•• ScreensScreens


Integrated Management SystemIntegrated Management System

IMSIMS

Quality Quality Management Management SystemSystem

DIN EN ISO 9001:2000DIN EN ISO 9001:2000

Environmental Environmental Management SystemManagement System

DIN EN ISO 14001:2005DIN EN ISO 14001:2005

Safety Safety & & Health Health Management SystemManagement System

Acc. to OHSAS 18001:1999Acc. to OHSAS 18001:1999

StörfallV StörfallV (SEVESO II)(SEVESO II)

96/82/EC + 2003/105/EC96/82/EC + 2003/105/EC

12. 12. BImSchV BImSchV -- 8.6.20058.6.2005


CertificatesCertificates


TBLS+TBLS+®® BatteriesBatteries FutureFuture

Volumen

Gewich

t

verfü

gbare

Kapaz

ität

Lade

zusta

nd

Stromau

fnahm

e bei

Kälte

Kaltsta

rtfähig

keit

010203040

-10-20-30-40

Veränderungen in %

Features of tomorrows battery (source: MOLL Batterien, Germany)

All features can be supported by TBLS+®

Volumen=Volume

Gewicht=Battery weight

Verfügbare Kapazität=Reserve capacity

Ladezustand=DoD or SoC

Stromaufnahme bei Kälte=Deep temp. recharge

Kaltstartfähigkeit=Cold cranking


Tri Basic vs. Tetra Basic CuringTri Basic vs. Tetra Basic Curing

4 Basic4 Basic Lead SulphateLead Sulphate::4.4.PbOPbO.PbSO.PbSO44Hard toHard to create thecreate the ‚‚seedingseeding‘‘ sitessites

low numberlow number of ‚of ‚seedsseeds‘‘largelarge crystals crystals fewfew largelarge poresporescuringcuring* time 2 * time 2 -- 4 h at T>80°C +4 h at T>80°C +steamsteamformationformation: : -- 450 450 –– 530 Ah / kg530 Ah / kg

-- rest phases during formationrest phases during formation

3 Basic3 Basic Lead SulphateLead Sulphate::3.3.PbOPbO.PbSO.PbSO44.H.H22OOEasyEasy toto create thecreate the ‚‚seedingseeding‘‘ sitessites

highhigh numbernumber of ‚of ‚seedsseeds‘‘small crystals small crystals many small poresmany small porescuringcuring* time 14 * time 14 –– 24 h at 55°C24 h at 55°Cformationformation: : -- 350 350 –– 400 Ah / kg400 Ah / kg

* Curing = the development of the final crystal structure* Curing = the development of the final crystal structure


„State of„State of thethe Art“: Art“: CuringCuring//DryingDrying

CuringCuring toto small sizedsmall sized 33 basic lead sulphate crystalsbasic lead sulphate crystals

TemperatureTemperature < 60°C:< 60°C:Crystal growth rateCrystal growth rate

slowslow: : 12 12 –– 24 h24 h timescaletimescalecrystal sizecrystal size: up to 3 µm: up to 3 µm

RiskRisk of of „„DryDry out“out“ ofof platesplates::caused by free lead contentcaused by free lead content ofof oxideoxide

combined with reactivity combined with reactivity ofof oxideoxidetypetype ofof millmill//reactor playsreactor plays aa roleroleoxide may needoxide may need toto be stored be stored

LoadingLoading timetime delays for platesdelays for platesexothermic oxidation reaction can exothermic oxidation reaction can

createcreate partial 4partial 4--basic structuresbasic structures


UseUse of of PowderPowder Seeding CrystalsSeeding Crystals

Addition ofAddition of drydry--milledmilled tetrabasic tetrabasic lead sulphate crystalslead sulphate crystals

SeedingSeeding crystals limitedcrystals limited to ca. 1to ca. 1--1.5 µm1.5 µmwithwith highhigh energy milling energy milling requirementsrequirements

Higher percentageHigher percentage ofof milled powder tetrabasic milled powder tetrabasic lead sulphate requiredlead sulphate required toto achieve desiredachieve desired finalfinalcrystal sizecrystal size ((can becan be 22--33 timestimes %% versusversus TBLS+TBLS+®®) )

WiderWider particle size distributionparticle size distribution ofof seed crystalsseed crystals ininpowderpowder form form less homogeneous crystal size less homogeneous crystal size distribution than with distribution than with TBLS+TBLS+®®

OperatorOperator hygiene issueshygiene issues associated with handlingassociated with handlingfinefine powders versuspowders versus TBLS+TBLS+®® liquid form liquid form


Wet milled Seeding CrystalsWet milled Seeding Crystals

Penox‘Penox‘ new approachnew approach::Wet millingWet milling ofof tetrabasic lead sulphate withtetrabasic lead sulphate with anan additiveadditive

Particle sizeParticle size ≤≤ 0.5 µm0.5 µmChemical separationChemical separation ofof the milled particlesthe milled particles toto avoidavoid rere--agglomerationagglomerationCuringCuring toto small sized tetrabasic lead sulphate crystalssmall sized tetrabasic lead sulphate crystals ininexisting curing chambersexisting curing chambers::

without steamwithout steam ((requiresrequires min. 6 h)min. 6 h)with steamwith steam (ca. 1(ca. 1--22 hourshours))

Advantages ofAdvantages of steam curingsteam curing::Reduced dependenceReduced dependence onon oxide qualityoxide quality44--basic crystal formationbasic crystal formation onon the plate is completethe plate is complete in c.1hin c.1hPrePre--requisite forrequisite for „„ConcureConcure“ (“ (continuous curingcontinuous curing andand dryingdrying))

0,1 1 10 100Grain Size [µm]

0102030405060708090

100[%]

TBLS+

Standard 4bs Sulphate


Nucleation Theory 1Nucleation Theory 1

Fluctuation theory:

Nucleation crystals grow and decay by the competing forces:

• Volume energy tends to grow the crystal EV (attractive energy)

• Surface energy tends to decay the crystal ES (dissolving energy)

Critical crystal size: EV = ES

Crystals > critical crystal size: survival and grow up

until exhaust of construction material

3PbOPbSO4 critical crystal size: small

4PbOPbSO4 critical crystal size: large


Nucleation Theory 2Nucleation Theory 2

Traditional curing:

Spontaneous genesis of nucleation crystals controlled by moisture,

temperature and recipe (amount of sulphuric acid)

• 4-basic lead sulphate:

low number of crystals due to large critical crystal size but of huge scale up to 50 µm

low BET surface but large pore sizes (low efficiency of active material)

costly and complex formation

• 3-basic lead sulphate:

high number of crystals due to low critical crystal size but of small size up to 3 µm

high BET surface but very small pore sizes (bad acid exchange)

easy and fast formation

Our new approach: control of 4-basic lead sulphate crystal sizes and pore sizes


Control of Particle Sizes 1Control of Particle Sizes 1

ControlControl of 4of 4 basic lead sulphate crystal size by basic lead sulphate crystal size by TBLS+TBLS+®® additionaddition

Base: no TBLS+TBLS+®® + 0.5% TBLS+TBLS+®®


Control of Particle Sizes 2Control of Particle Sizes 2

ControlControl of 4of 4 basic lead sulphate crystal size by basic lead sulphate crystal size by TBLS+TBLS+®® additionaddition

+ 1.5% TBLS+TBLS+®® + 3.0% TBLS+TBLS+®®


Theoretical Estimation Theoretical Estimation of Crystal of Crystal SizeSize


Powder vs. SlurryPowder vs. Slurry

Crystal sizeTBLS+® vs Dry Sulphate (kg vs kg)

0

10

20

30

40

50

60

70

80

0,50% 1,00% 1,50% 2,00%

% TBLS+® / Powder added

Theo

retic

al c

ryst

al s

ize

(mic

rons

)

TBLS-6 LPowder-6LTBLS-8LPowder-8LTBLS-10LPowder-10L


TBLS+TBLS+®® -- QC QC ProceduresProcedures

TBLS+® is an Added Value Product therefore it needs advanced QC Procedures

Raw Material Control Procedures

- IR Analysis (tri/tetrabasic content)

In-Process Control Procedures- IR Analysis (tri/tetrabasic content)- pH-value- Particle size (Laser Diffraction)- Solids content

Final Product Control Procedures- IR Analysis (tri/tetrabasic content)- Particle size (Laser Diffraction)- Solids content- Density- Total Pb- Iron content

Bulk Material (dry powder)

Milling Step

-Addition of demineralised water

-Addition of Anti-Agglomerate Material

TBLS+® (approx. 40%* solids)packed into container or small buckets according to customer demands*depending on seeding crystal content


TBLS+TBLS+®® GridGrid Basics 1Basics 1

Features of different battery typesUntil 1990 batteries are mainly produced with Sb alloys for pos. and neg. plates. These alloys forced self-discharge and water consumption.

The next production step was the use of Ca alloys for pos. and Sb alloys for neg. plates. This step improved the self-discharge and water consumption moderately. This type of batteries is known as Hybrid batteries.

Today the use of Ca alloys for pos. and neg. plates is usual. Thesealloys gave the best results for battery performance but need some improvement for the curing/drying.


TBLS+TBLS+®® GridGrid Basics 2Basics 2

Antimony free effect for Ca alloysDeep discharge of Ca alloy grids leads to bad or impossible recharge of the battery. Also capacity losses > 50 % DOD can occur.

Reasons are:

- Formation of a non conductive CaSO4-layer between grid and PAM

- Formation of non conductive PbSO4 in the paste without any remaining PbO2

- Bad grid/paste adhesion

Technical options to avoid the antimony free effect

- Addition of higher amounts of Sn to the Ca alloy

- Curing to tetrabasic lead sulphate. Tetrabasic PbSO4 gives more alpha PbO2. Alpha PbO2 is harder to convert into PbSO4 during discharge of the battery than beta PbO2 (beta PbO2 was easily formed out of tribasic PbSO4) . The remaining conductive alpha PbO2 helps to recharge the battery again.


Application of TBLS+Application of TBLS+®®

Add Add TBLS+TBLS+®® to the to the leady leady oxideoxide atat thethe start ofstart of paste mixingpaste mixing

0.5 to 3 0.5 to 3 % % TBLS+TBLS+®® slurry slurry to the to the leady leady oxide oxide –– no change to customer recipe* no change to customer recipe*

1 h steaming of plates in stacks at > 80°C / high humidity (for1 h steaming of plates in stacks at > 80°C / high humidity (formation of TTBLS)mation of TTBLS)

dependent upon local requirements dependent upon local requirements -- 2 options:2 options:-- cure for 4cure for 4--6 h then dry 6 h then dry OROR

-- immediately start drying immediately start drying (with good air circulation to allow free lead reduction)(with good air circulation to allow free lead reduction)

(high free lead content in the oxide will speed up the drying (high free lead content in the oxide will speed up the drying process)process)In batch chambers <12h drying timeIn batch chambers <12h drying timeIn CONCURE chamber < 1In CONCURE chamber < 1-- 2 h drying time2 h drying time

* With experience, small changes in the recipe (e.g. acid:oxide ratio) can be introduced to maximise the benefits


TBLS+TBLS+®® CuringCuring BasicsBasics

Curing – State of the Art

- Use of big sized chambers without steam

- Temperature and humidity are hard to control

- Long loading times lead to dryout effects and gave bad lead reduction

- Bad grid/paste adhesion for „anticorrosive“ grids (Pb/Ca/Sn, Ag9,...)

- Long curing and drying processes (24 – 36 h for curing; 24 – 48 h for drying)

Why Steam Curing?

- Use of smaller sized chambers

- Easy control of temperature and humidity

- Shorter loading times

- Max. 3 h curing time (Arrhenius Law) gives an increase of curing capacity

- Improved paste/grid adhesion for all types of grids

- Important for neg. plates to improve porosity by use of TBLS+®


TBLS+TBLS+®® -- Commercial AdvantagesCommercial Advantages

SavingSaving of positiveof positive activeactive materialmaterialReductionReduction ofof activeactive positive materialpositive material byby > 4 %> 4 %Higher porosityHigher porosity andand improved homogenaity leadimproved homogenaity lead to ato a significant increasesignificant increase inin the the active mass utilisationactive mass utilisation reductionreduction inin the paste densitythe paste density // massmass perper plate for the plate for the same capacitysame capacity

TBLS+® offers advantages versusoffers advantages versus ::

SmallSmall sized sized tribasic lead sulphate crystal structurestribasic lead sulphate crystal structures ::Higher capacityHigher capacity andand cold cranking during cyclingcold cranking during cyclingLess dependenceLess dependence onon oxide qualityoxide quality andand shorter curingshorter curing//drying process drying process

BigBig sized sized tetrabasic lead sulphate crystal structuretetrabasic lead sulphate crystal structure ::ReductionReduction ofof electrical energy required for formation byelectrical energy required for formation by >25%>25%ReductionReduction ofof formation formation timetime byby > 12 h> 12 h typically typically Less overheating during formationLess overheating during formation


TBLS+TBLS+®® NewNew DevelopmentsDevelopments 11

Curing and drying of negative plates

Formation of tetrabasic PbSO4 in presence of Vanisperse

020

406080

100120

0

0,01

0,02

0,03

0,04

0,05

0,06

0,07

0,08

0,09 0,1

w(Vanisperse) in %

Tet

rab

asi

c co

nte

nt

in %

Std. neg. plateNeg. plate with TBLS+

Expanders (e.g. Vanisperse) prevent negative plates from becoming converted to 4 basic leadsulphate crystals• 3 basic lead sulphate crystals exhibit smallpore and crystal sizes• Limit state of discharge due to blocking of poresFor the first time TBLS+® makes it possible to control the crystal and pore sizes of negative plates still using expanders:• Increase of pore volume• Deeper discharge nevertheless keepinglifetime requirements• Reducing the mass shedding of negative active material• Improvement of negative plates to fit to theprogress of positive plates

Test procedure:

Steaming 95°C, 100 % rel H, 3 hours

Std. plates and plates with 1.5 % TBLS+®



Managing of pore and crystal sizes of negative plates by use of TBLS+®

Add of 1.5 % TBLS+® , 0.05 % Vanisperse and 3 h steaming

Negative plate coming from normal production

In the face of expanders: 4 basic lead sulphate crystals using TBLS+®



In the face of expanders: 4 basic lead sulphate crystals using TBLS+®

Add of 1.5 % TBLS+® , 0.05 % Vanisperse and 3 h steaming

Negative plate coming from normal production

X-Ray investigations of negative plates by use of TBLS+®



Porosity investigations of negative plates by use of TBLS+®

Mercury porosity measurement gives the following results

Pore sizes

Std. plate: 0.2 µm

TBLS+®: 3.0 µm

Intrusion values for 5 sec. Mercury intrusion

Std. plate: 0.11 ml/g

TBLS+®: 0.44 ml/g



Formed neg. plate coming from normal production (0.1 % Vanisperse)

In the face of expanders: formed negative plates using TBLS+®

Managing of pore and crystal sizes of negative plates by use of TBLS+®

Formed neg. plate with 1.5 % TBLS+®

0.05 % Vanisperse and 3 h steaming



Pore and crystal sizes of formed negative plates by use of TBLS+®

Results of Hg-Porosimetry

Total Intrusion Volume

Std. plate: 0.097 ml/g

TBLS+®: 0.120 ml/g

Avrg. Pore Diameter

Std. plate: 0.283 µm

TBLS+®: 0.377 µm

Porosity

Std. plate: 44.6 %

TBLS+®: 53.2 %

Summary: Improved cold cranking values (+ 25 %)


TBLS+TBLS+®® Results Results 1 (Ind. 1 (Ind. BatteriesBatteries))


TBLS+TBLS+®® ResultsResults 2 (Ind.2 (Ind. BatteriesBatteries))


TBLS+TBLS+®® Results Results 33

Attention Attention –– There is There is no no redesign redesign of of the plates the plates ((by less active by less active material) material) or theor the

batteriesbatteries ((by leaving away one plate by leaving away one plate per per cellcell).).


What will TBLS+What will TBLS+®® finally offer ?finally offer ?


How can PENOX GmbH assist ?How can PENOX GmbH assist ?

tbls+ general presentation–apr. 2008/ik cert.-no.: de ...general presentation-apr2008-ik.pdfpenox...

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