CAT HODE OPT IMIZING SOL UT ION OPT I MI ZE YOUR CHL OR - - - PowerPoint PPT Presentation

CAT HODE OPT IMIZING SOL UT ION

OPT I MI ZE YOUR CHL OR - AL K AL I ME MBRANE CE L L

CONF IDE NT IAL

By Dino DiF ra nc o

About Me

• B.S./ M.S. in Che mic a l E

ng ine e ring fro m CWRU with a spe c ia lty in E le c tro c he mistry

• Ma ste r’ s T

he sis in E le c tro pla ting

• Spe nt 12 ye a rs wo rking in e le c tro pla ting a va rie ty o f ma te ria ls fo r a

F

• rtune 100 e le c tro nic s c o mpa ny (Cathode F
• c use d)

 Co ppe r  Nic ke l  Go ld  Silve r  T

in

 L

e a d-tin so lde r

 Bra ss  Chro mium  Pla tinum  Zinc  Zinc -nic ke l  e tc .

• Autho r o n 30+ Pa te nts
• Winne r o f a n R&D 100 Awa rd

CONF I DE NT I AL

About Me : (Continue d)

• Jo ine d E

L T E CH Syste ms / De No ra fo r 20 ye a rs (Anode F

• c use d)
• T

he se c o mpa nie s c o mme rc ia lize d He nri Be e r’ s histo ric 1968 Ano de inve ntio n whic h is a the rma lly a pplie d mixe d me ta l o xide o n tita nium.

• He nri Be e r’ s inve ntio n o f using me ta l o xide s a s a n a no de in a n o xidizing

e nviro nme nt de live rs e xc e ptio na l pe rfo rma nc e a nd c a n de live r 25+ ye a rs

• f se rvic e witho ut a ppre c ia b le vo lta g e e sc a la tio n.
• While it c a n a lso func tio n a s a c a tho de , this te c hno lo g y is no t o ptimum fo r c a tho de s

whic h a re in a re duc ing e nviro nme nt. L imita tio ns inc lude :

• Vo lta g e e sc a la tio n
• Po o r a dhe sio n
• Hig h we a r ra te
• L

imite d life time I be lie ve the r e is r

• om to impr
• ve

c hlor

• alkali c athode s and this is one of the

r e asons I star te d E le c tr

• de Solutions.

CONF I DE NT I AL

Cr ac ks and Por e s in a T he r mally Applie d Coating

• Re q uire Po la riza tio n
• Po o r sub stra te pro te c tio n
• Hig h c o st
• So me a re a s no t a c tiva te d

IN- SIT U CAT HODE ACT IVAT ION BE NE F IT S

• No Ca tho de Re c o a ting

 No c e ll dis-a sse mb ly  No shipping o f c a tho de s  No spa re c a tho de re q uire me nts (I

dle c a pita l)

 No c a tho de disto rtio n o r thinning fro m re c o a ting  No c a tho de wa rra nty c o nstra ints / c o nc e rns  No la rg e c a pita l e xpe nse fo r re c o a ting

• Ope ra te a t the L

OWE ST E NE RGY CONSUMPT ION

 Ac tiva te a ll a re a s c a pa b le o f hydro g e n e vo lutio n  No vo lta g e e sc a la tio n (c o nsiste nt c e ll ro o m pe rfo rma nc e )  I

mme dia te re c o ve ry fro m upse ts

• MUCH L

E SS e xpe nsive a nd BE T T E R tha n OE M supplie d c a tho de c o a ting s

• Po ssib le impro ve me nt fo r the me mb ra ne

 E

q uilib ra te the c urre nt de nsity a c ro ss the me mb ra ne surfa c e

 L

e ss he a ting a t the me mb ra ne surfa c e = Highe r

E ffic ie nc y

 L

e ss hydro g e n o n the me mb ra ne = L

• we r

H2 in Cl2 CONF I DE NT I AL

Voltage T ime On- L ine

OE M Cathode War r anty

IN- SIT U CAT HODE ACT IVAT ION – Histor y

• So me OE

M’ s ha ve pro mo te d in-situ a c tiva tio n in the pa st (CE C, E L T E CH, e tc ).

• I

pro mo te d a pro duc t c a lle d VRS (Vo lta g e Re duc tio n So lutio n) fo r E L T E CH in the e a rly 2000’ s.

• Ma ny c usto me rs use d it in the ir c e ll ro o ms
• Vo lta g e re duc tio n wa s o b se rve d using VRS (T

e c hnic a l suc c e ss)

• E

c o no mic s o f using VRS we re no t sa tisfa c to ry (E c o no mic fa ilure )

VRS wa s to o e xpe nsive b ut it de mo nstra te d the pro mise o f a b e tte r c a tho de via in-situ a c tiva tio n.

CONF I DE NT I AL

IN- SIT U CAT HODE ACT IVAT ION – T ODAY CAT HODE OPT IMIZING SOL UT ION (COS) wa s de ve lo pe d to de live r o ptimize d

c a tho de pe rfo rma nc e a t a n e c o no mic pric e . COS is a dde d in-situ to the c a tho lyte a nd imme dia te ly a c tiva te s a ll surfa c e s c a pa b le

• f hydro g e n e vo lutio n.
• Surfa c e s pre vio usly a c tiva te d a re re ne we d

COS is e c o no mic a l e no ug h tha t it is c o ntinuo usly a dde d to ma inta in the lo we st e ne rg y c o nsumptio n a nd a c hie ve a sta b le c a tho de pe rfo rma nc e . Unlike the rma lly a pplie d c o a ting s pro vide d b y OE M’ s, COS will se a l o ff the unde rlying nic ke l a nd pro te c t the nic ke l sub stra te during po we r o uta g e s.

CONF I DE NT I AL

Catalyst Non-Catalyst, Binder, Filler

NICKEL METAL SUBSTRATE

Oxide Coating

Voids Cracks

COS Coating

Catalyst

NICKEL METAL SUBSTRATE

CONF I DE NT I AL

T

• a vo id vo lta g e e sc a la tio n,

the c o a ting must pro te c t the unde rlying nic ke l a nd b e a dhe re nt. T his is e spe c ia lly impo rta nt during o uta g e s.

COS is a dhe re nt to the nic ke l

sub stra te a nd pro te c ts it.

CONF I DE NT I AL

Po ro us OE M Ca tho de Co a ting a llo ws c o rro sio n a nd c o rro sio n pro duc ts (g re e nish c o lo r) to mig ra te to the surfa c e .

COARSE MESH (ACTIVATED) ANODE (ACTIVATED) MEMBRANE A N O L Y T E C A T H O L Y T E CHLORINE GAS HYDROGEN GAS

E ARL Y CHL OR-AL K AL I ME MBRANE CE L L S WE RE DE SI GNE D WI T H A F I XE D GAP BE T WE E N T HE CAT HODE AND T HE ME MBRANE T O PRE VE NT ME MBRANE DAMAGE . T HE SE CE L L S ARE RE F E RRE D T O AS “F I XE D GAP” CE L L S.

FIXED GAP CHLOR-ALKALI MEMBRANE CELL

CONF I DE NT I AL

COARSE MESH (ACTIVATED) ANODE (ACTIVATED) MEMBRANE A N O L Y T E C A T H O L Y T E CHLORINE GAS HYDROGEN GAS

I N A F I XE D GAP CE L L , T HE HYDROGE N GAS I S E VOL VE D ON T HE ACT I VAT E D COARSE ME SH AS SHOWN HE RE .

FIXED GAP CHLOR-ALKALI MEMBRANE CELL

CONF I DE NT I AL

COARSE MESH (NOT ACTIVATED) ANODE (ACTIVATED) MEMBRANE A N O L Y T E C A T H O L Y T E CHLORINE GAS HYDROGEN GAS

NE WE R CE L L DE SI GNS AND/ OR RE T ROF I T S OF OL DE R CE L L S I NCORPORAT E A ZE RO GAP DE SI GN WHE RE I N A COMPRE SSI BL E L AYE R I S PL ACE D BE T WE E N T HE COARSE ME SH AND A F I NE SCRE E N.

ZERO GAP CHLOR-ALKALI MEMBRANE CELL

FINE MESH (ACTIVATED) COMPRESSIBLE LAYER (NOT ACTIVATED)

CONF I DE NT I AL

COARSE MESH (NOT ACTIVATED) ANODE (ACTIVATED) MEMBRANE A N O L Y T E C A T H O L Y T E CHLORINE GAS HYDROGEN GAS

I N A ZE RO GAP CE L L , T HE F I NE ME SH I S ACT I VAT E D AND T HE HYDROGE N GAS I S E VOL VE D ON T HE F I NE ME SH ONL Y.

ZERO GAP CHLOR-ALKALI MEMBRANE CELL

FINE MESH (ACTIVATED) COMPRESSIBLE LAYER (NOT ACTIVATED)

CONF I DE NT I AL

MORE T HAN 2/ 3 r

ds OF

T HE AVAI L ABL E CAT HODE SURF ACE ARE A I S NOT

ACT IVAT E D I

N PRE SE NT DAY ZE RO GAP CE L L S.

COARSE MESH (NOT ACTIVATED) ANODE (ACTIVATED) MEMBRANE A N O L Y T E C A T H O L Y T E CHLORINE GAS HYDROGEN GAS

ZERO GAP CHLOR-ALKALI MEMBRANE CELL

FINE MESH (ACTIVATED) COMPRESSIBLE LAYER (NOT ACTIVATED)

CONF I DE NT I AL

COARSE MESH (ACTIVATED) ANODE (ACTIVATED) MEMBRANE A N O L Y T E C A T H O L Y T E CHLORINE GAS HYDROGEN GAS

ZERO GAP CHLOR-ALKALI MEMBRANE CELL BY ELECTRODE SOLUTIONS

FINE MESH (ACTIVATED) COMPRESSIBLE LAYER (ACTIVATED)

AF T E R T HE ADDI T I ON OF CAT HODE OPT IMIZING SOL UT ION F ROM E L E CT RODE SOL UT I ONS, AL L SURF ACE S I N T HE CAT HOL YT E ARE ACT I VAT E D AND E VOL VI NG HYDROGE N GAS, AND T HE CE L L VOL T AGE I S RE

DUCE D! CONF I DE NT I AL

COARSE MESH (ACTIVATED) ANODE (ACTIVATED) MEMBRANE A N O L Y T E C A T H O L Y T E CHLORINE GAS HYDROGEN GAS

ZERO GAP CHLOR-ALKALI MEMBRANE CELL BY ELECTRODE SOLUTIONS

FINE MESH (ACTIVATED) COMPRESSIBLE LAYER (ACTIVATED)

1 1.05 1.1 1.15 1.2 1.25 1 2 3 4 5 6 7 8 9 10

CATHODE VOLTAGE

kA/m2

Cathode Voltage vs Current Density

CAT HODE OPT IMIZING SOL UT ION OPT I MI ZE S T HE CAT HODE OPE RAT I ON. PRE VI OUSL Y UNACT I VAT E D SURF ACE S ARE ACT I VAT E D AND PRE VI OUSL Y ACT I VAT E D SURF ACE S ARE RE NE WE

• D. T

HE CAT HODE CURRE NT DE NSI T Y I S L OWE RE D.

CONF I DE NT I AL

CONF I DE NT I AL

Imme diate r e sults with COS.e

COS F IE L D DAT A

OT HE R BE NE F IT S OF A CAT AL YZE D CUSHION L AYE R

OE M supplie d c a ta lyze d fine me sh la ye rs inc re a se the te mpe ra ture o f the me mb ra ne b y a t le a st 5 oC a c c o rding to AGC c he mic a ls whic h lo we rs the Curre nt E ffic ie nc y b y 0.5-1%. Ca ta lyzing the c ushio n la ye r c o unte rs the se ne g a tive e ffe c ts a nd impro ve s the o pe ra tio n.

CONF I DE NT I AL

AGC da ta pre se nte d a t Clo ro sur T e c hnic a l Se mina r

OT HE R BE NE F IT S OF A CAT AL YZE D CUSHION L AYE R

OE M supplie d c a ta lyze d fine me sh la ye rs inc re a se the hydro g e n in c hlo rine . Ca ta lyzing the c ushio n la ye r with COS c o unte rs this ne g a tive e ffe c t a nd impro ve s the o pe ra tio n.

CONF I DE NT I AL

AGC da ta pre se nte d a t Clo ro sur T e c hnic a l Se mina r

HOW T O ADD COS

Addition Setup To Electrolyzer COS diluted 20:1 with 32 wt% Caustic

Caustic Recirculation Line

Metering Pump

CONF I DE NT I AL

Phase Time Period Finite Gap Zero Gap 1 24-48 hours 5 - 15 ml/m2 20 - 40 ml/m2 2 24-48 hours 0 - 5 ml/m2 0 - 10 ml/m2 3 Continuous 0.5-2.5 ml/m2 - week 0.5-2.5 ml/m2 - week

COS L AB DAT A

Trial Coarse Cushion Fine A Bare Nickel Bare Nickel Bare Nickel B Bare Nickel Bare Nickel Catalyst C Catalyst Bare Nickel Catalyst D Catalyst Catalyst Catalyst

CONF I DE NT I AL

Me mbr ane F ine Cushion Coar se

CONF I DE NT I AL COS F IE L D DAT A

(E L T E CH E xL1.5 m2 Ce lls)

COS lo we re d the vo lta g e o f e a c h c e ll b y ~90 mV. COS lo we re d the vo lta g e o n thre e diffe re nt re c e ntly insta lle d OE M c a tho de c o a ting s b y 20-30 mV. COS Sa ving s re ta ine d a fte r un-pro te c te d 6 ho ur po we r o uta g e . Minimum Vo lta g e a t ~10 ml/ m 2 o f COS

CONF I DE NT I AL COS F IE L D DAT A

(UHDE 2.7 m2 BiPolar Ce lls)

COS lo we re d the vo lta g e o f e a c h c e ll b y ~50 mV. COS Sa ving s re ta ine d a fte r po we r o uta g e . Minimum Vo lta g e a t ~4 ml/ m2 o f COS

T AK E N F ROM T HE DE NORA WE BSI T E

CONF I DE NT I AL

COS

CONF I DE NT I AL E CONOMICS (Daily) Cells in yellow can be changed

Electrolyzer Characteristics Number of Electrolyzers: 8 Cathodes per Electrolyzer: 94 Total # of Cathodes: 752 M2 per Cathode: 2.7 Total Cathode M2: 2030.4 COS Requirements Initial Addition: 14 ml/m2 Continuous Additions 0.5 ml/m2-week COS Price: $0.720 per ml Initial Addition Cost $20,466 Continuing Addition Cost $104 $/day Voltage Savings Average Savings from COS: 0.100 Volts Current Density 5.00 kA/m2 Power Costs $0.060 per kWH Rectifier efficiency 95.0 % Savings

ROI is 15 Days

Savings per day with COS $1,538.83 $/day

COS Savings Analysis

($100,000) $0 $100,000 $200,000 $300,000 $400,000 $500,000 $600,000 50 100 150 200 250 300 350 400

Days On-Line

Savings vs Days On-line

E CONOMICS (With Capital) CONF I DE NT I AL

Cells in yellow can be changed

Electrolyzer Characteristics Number of Electrolyzers: 8 Cathodes per Electrolyzer: 94 Total # of Cathodes: 752 M2 per Cathode: 2.7 Total Cathode M2: 2030.4 COS Requirements Initial Addition: 14 ml/m2 Continuous Additions 0.5 ml/m2-week COS Price: $0.720 per ml Initial Addition Cost $20,466 Continuing Addition Cost $104 $/day Voltage Savings Average Savings from COS: 0.100 Volts Current Density 5.00 kA/m2 Power Costs $0.060 per kWH Rectifier efficiency 95.0 % Savings Savings per day with COS $1,538.83 $/day

COS Savings Analysis

1 2 3 4 5 6 7 8 29 48 66 85 104 123 141 160 1 2 3 4 5 6 7 8 277 553 830 1107 1383 1660 1936 2213 1 2 3 4 5 6 7 8 1200 1 2 3 4 5 6 7 8 1448 1706 1964 2221 2479 2737 2995 3253 YEAR #3: Conventional Recoating Cost Saving ($/m2) YEAR TOTAL SAVINGS After COS Conversion ($/m2) (#3 + #2 - #1) #1: Accumulated Expense After COS Conversion ($/m2) YEAR YEAR #2: Accumulated Energy Savings After COS Conversion ($/m2)

CONF I DE NT I AL

OT HE R POSSIBL E BE NE F IT S F ROM COS

• I

nc re a se pro duc tio n o r a dd a dditio na l c e lls if pre se ntly re c tifie r limite d.

• I

nsta ll lo ng e r life a no de s

• Minimize a no de re c o a ting whic h c a n ha rm the a no de e le me nts
• A 2 x life a no de is o nly ma rg ina lly mo re c o stly tha n a 1x life a no de .
• Ac hie ve lo ng e r me mb ra ne life b y impro ving the c urre nt

unifo rmity a c ro ss the me mb ra ne a nd re duc ing me mb ra ne

• ve rhe a ting .
• L
• we r nic ke l c o nta mina tio n o f the me mb ra ne .
• L
• we r CO 2 fo o tprint
• E

a sy, I ne xpe nsive o n-site c o nve rsio n to ze ro -g a p te c hno lo g y

CONF I DE NT I AL

CAT HODE OPT IMIZING SOL UT ION (COS):

• E

liminate s Conve ntional Cathode Re - Coating

 No Downtime  No Spar

e Cathode s r e quir e d

 No Cr

ating and Shipping of Cathode s

• Re c ove r

lost Cathode Pe r for manc e

• De live r

s a lowe r voltage than OE M Cathode Coatings

 ~30 mV savings on OE

M c oatings

 200+ mV savings on ze r

• - gap c e lls
• Pr
• te c ts the nic ke l substr

ate be tte r than OE M Cathode Coatings

• Pr
• te c ts and ac tivate s all sur

fac e s on the nic ke l c athode

• E

asy and Safe to use

• Doe s not har

m c e ll r

• om c ompone nts
• Doe s not c ontaminate the c austic pr
• duc t
• Cor

r e c ts me mbr ane ove r

• he ating obse r

ve d in ze r

• gap c e lls utilizing OE

M ze r

• gap c athode s.
• Highe r

c e ll e ffic ie nc y

• L
• we r

H2 in Cl2

• Ve r

y E c onomic al to use

• Pe r

for manc e is mostly r e taine d afte r powe r

• utage s
• No war

r anty c onc e r ns

CONF I DE NT I AL

OEM Coating COS Cost ~$1000/m2 ~$10/m2  Stable Coating No Yes  Requires a Cell Room Outage/Downtime to Install Yes No  Requires Dis-assembly to install Yes No  Requires Shipping Yes No  Requires Cathode Spares Yes No  Recover From Upsets No Yes  Activate All Available Cathode Area No Yes  Require Polarization to Protect Coating Yes No  Adequately Protects the Nickel Substrate No Yes  Contaminates the Caustic Product Yes No  Removeable via Tape or a Water Hose Yes No  Delivers the Lowest Energy Consumption No Yes  Corrects Membrane Over-Heating in Zero Gap Cells No Yes  Warranty Requirements Yes No 

E ve n if a n OE M o ffe rs

F RE E CAT HODE COAT ING, yo u

a re still b e tte r se rve d with

COS

fro m E le c tro de So lutio ns.

CAT HODE OPT IMIZING SOL UT ION

CONF I DE NT I AL