31 new interesting applications for ccp_sw tes seminar

New Interesting Applications for CCP-Specialized Water :

Selective Fluoride- and Ammonia-Adsorption

Dr. Stefan Neumann Manager Technical Marketing, Ion Exchange Applications

- IX Seminar, TES, 2008_06_05 -

Preamble: Problem and Task-Description

New Interesting Applications for CCP-SWDr. Stefan Neumann, mai 20083

Selectivity of Strongly Basic Anion IX (SBA)

ClO4- >

Me(CN)xy- >

MeClxy- >

I- >CrO4

2- >SO4

2- >Br- > CN- >HSO4

- >NO3

- >Cl- >H2PO4

- >F- >H2BO3

- >HCO3

- >OH- >HSiO3

-

Selectivity of Strongly Acidic Cation IX (SAC)

Ba2+ >Pb2+ >Sr2+ >Ca2+ >Ni2+ >Cd2+ >Cu2+ >Co2+ >Zn2+ >Fe2+ >Mg2+> Mn2+ > Alkalis >NH4

+> H+

Problem: For some ions selective adsorption on conventional IX is not possible !

Selectivity

Selectivity


Problem: To adsorb non selective ions means that all the more selective ions have to be adsorbed too !

adsorption zonefor highly selective ions

adsorption zonefor less selective ions

For the adsorption of less selective ions, all higher selective ions have to be adsorbed too!


Challenge / Task Description:

newselective IX-adsorbers forF- and NH4+

required !

Fluoride Removal – by Al-doped Lewatit® TP260


Task Description

• Waste Water: Limits for fluoride in waste water are locally very different. Limit of 1ppm (Vietnam), Limit of 5 ppm (Thailand, USA), …

Relevant Industries: Mining, Metal Refining, Metal Finishing, Solar Industry,

Computer Chip Industry, Ceramic Industry, ….

• Potable Water: Limit in Germany for Fluoride is 1,5 ppm, in USA 2 …4 ppm

Groundwater: … can contain up to 10 ppm of fluoride

Fluoride removal is frequently requested by IX customers

Fluoride Removalby Al-doped Lewatit TP260


Lewatit TP 260 in Al-Form

Type: AMPA-Harz in Al-FormAluminia-Load: > 1,0 mol/LDoping: by end-user

Cl

AlCH2 - N

H

=

CH2-P-O

O

O

Product DescriptionFluoride Removal

by Al-doped Lewatit TP260


Cl

AlCH2 - N

H

=

CH2-P-O

O

O + F-

AlCH2 - N

H

=CH2-P-O

O

OF-

+ Cl-

Na

CH2 - NH

=

CH2-P-O

O

O

+ 4 NaOH, - [Al(OH)4-], - NaF

Exhaustion:

Regeneration:

+ AlCl3

Conditioning:

112 g AlCl3 per liter ofresin

Na

Process DescirptionFluoride Removal

by Al-doped Lewatit TP260


0

200

400

600

800

1000

1200

0 50 100 150 200 250 300

t (min)

Konz

entr

atio

n (m

g/L)

Fluorid

Chlorid

Sulfat

Nitrat

Uptake of6,4 g (0,33 mol)fluoride perlitre of resin

Exchange of F- versus Cl-

No uptake ofNO3

-, SO42-

Adsorption Kinetik Test: 25 ml of resin suspended in 200 ml solution

Fluoride Removalby Al-doped Lewatit TP260Chemistry


Break Through Curves -selective and non selecitve IX adsorbers


Operating Conditions: 1,3 moles of Al doped per litre of resin Lewatit TP260, (resin pH = 2)MP62 and MP500 in Cl-form, SV= 10 BV/h,

pH of feed solution 3.7, anions content: 1.5 g/L Cl- and 1.9 g/L SO4

2-, 0,13 g/L F-


Break Through Curves -at different feed concentrations

Fluoride Concentration in

Colum

n Outlet (ppm

)

Throughput (BV)

Operating Conditions: SV= 10 BV/h, 1,3 moles of Al doped per litre of resin Lewatit TP260,

pH of resin, pH of feed solution 3.7, demin water,

fluoride concentration as given above



Break Through Curve -at low feed concentration of fluoride

Fluoride Concentration in

Colum

n Outlet (ppm

)

Throughput (BV)

Operating Conditions: SV= 10 BV/h, 1,3 moles of Al doped per litre of resin Lewatit TP260 pH of feed solution 3.7, demin water with 4.76 ppm F- in the feed,



Fluoride Uptake -as a function of F- feed concentration

Fluoride Uptake of R

esin in Equilibrium

(g/L)

Fluoride Concentration in Feed (mg/L)

Operating Conditions: SV= 10 BV/h, 1,3 moles of Al doped per litre of resin Lewatit TP260 pH of feed solution 3.7, demin water with 100 ppm F-,



Aluminia-Leakage from theResin


Operating Conditions: SV= 10 BV/h, 1,3 moles of Al doped per litre of resin Lewatit TP260 pH of feed solution pH=3.7, demin Water,


Fluoride Uptake -as a function of F- feed concentration


esin in Equilibrium

(g/L)

Fluoride Concentration in Feed (mg/L)

Operating Conditions: SV= 10 BV/h, 1,3 moles of Al doped per litre of resin Lewatit TP260 pH of feed solution 3.7, Demin Water,



Fluoride uptake -as a function of pH in feed solution


esin (g/L)

pH in feed solution

Operating Conditions: SV= 10 BV/h, 1.2 moles of Al doped per litre of resin Lewatit TP260 Demin Water, cF-,feed: 127 mg/L




Fluoride uptake -as a function of NaCl content in feed

salt content in solution (g/L)


esin (g/L)

Operating Conditions: SV= 10 BV/h, 1.5 moles of Al doped per litre of resin Lewatit TP260,

salt content: 50% p.w. NaCl + 50% p.w. Na2SO4, total salt content as given above, cF-,feed: 80 mg/L, pH in feed solution: pH =3,6



Fluoride uptake -as a function of hydraulic load


esin (g/L)

specific flow rate (BV/h)

Operating Conditions: SV= 10 BV/h, 1.2 moles of Al doped per litre of resin Lewatit TP260 feed solution: demin water, cF-,feed: 100 mg/L, pH =3,7



Fluoride uptake -as a function of resin pH -conditioning

Operating Conditions: SV= 10 BV/h, 1.3 moles of Al doped per litre of resin Lewatit TP260 feed solution: demin water, cF-,feed: 100 mg/L, pH =3,8

pH established at resin conditioning


esin (g/L)



Regeneration: Grade of Regeneration

Grade of R

egeneration (%)

volume of NaOH solution pumped into the column (BV)



Summary

Selective removal of fluoride from aqueous solutions proofed principally feasible

Maximum uptake of resin up to 15 g of fluoride per litre of resin, under „normal“ conditions 5 to 10 g/l to be expected

Leakage is around 10% of feed concentration

Al leakage from resin relatively high in starting phase, Al-leakage negatively impacts fluoride uptake

Fluoride uptake of resin decreases with a) decreasing fluoride concentrationb) increasing pH

Fluoride uptake of resin increases with a) increasing salt contentb) increasing specific velocity

XX

XX

X

X

X Regeneration possible

X Resin conditioning important for process efficiency, furtherdevelopment and process optimisation should start here

Σ=…



Open Questions

Why has salt content in solution a positive impact on fluoride uptake ?

Is there a difference between impact of SO42- and Cl- ?

How to adapt process to potable water requirements?

Over all efficiency of the process?

?

???

?

How to reduce Al leakage from the resin ? Modify conditioning procedure?

? Will another resin type give better results ?

? Why is fluoride uptake of resin so low compared to theory? (theory > 20 g/L)

? Benchmark with competing process such as activated aluminia adsorption?



Application Status

Process still to be regarded as a „Process in Development“

!

!

3 Reference plants lately built but no technical data and feed-back so far available!

! Process so far only applicable for waste water treatment. For potable water still too many open question left.

NH3-Removal by Cu-doped Lewatit CNP80


Task Description Ammonia Removalby Cu-doped Lewatit CNP 80

• Waste Water: Limits for NH4 in waste water are locally very different. Limit of 25 ppm in Germany …

Relevant Industries: Fertilizer Plants, Waste Incinerator Plants, Bio-Gas-

Producers, Agriculture, ….

• Potable Water: Limit of 1 ppm in potable water (German TrinkWV 2001)

Ammonia removal is frequently requested by IX customers


Lewatit CNP80 in Cu-Form

Cu2+

Product Description Ammonia Removalby Cu-doped Lewatit CNP 80

C-O

=O

2

-

Type: weakly acidix IX-resin in Cu-formCu-Load: > 1,0 mol/LDoping: by end-user


Ammonia Removalby Cu-doped Lewatit CNP 80Chemistry

NH4 + <–> NH3 + H+

0

10

20

30

40

50

60

70

80

90

100

0 2 4 6 8 10 12 14

pH

% N

H 3 a

s a

part

of (N

H4+ +

NH 3

)

Ammonia only exist in aqueous solution at pH > 8!


Ammonia Removalby Cu-doped Lewatit CNP 80Chemistry

N

HHH

Cu2+

NHH

N HHHNH

H H

H

stronlgy blue colored copper-tetraamin-complex

4 NH3 + Cu2+a.q.

aq.


+

Regeneration: e.g.

+ 3 HCl- 3 NH4Cl

Cu2+ 3 NH3C-O

=O

2

-

Cu2+

NH 3

C-O

=O

2

-

NH3

Exhaustion:

Process Description Ammonia Removalby Cu-doped Lewatit CNP 80

NH3


Ammonia Removalby Cu-doped Lewatit CNP 80

Comparison of differentResin Types

P CH2

CH2

NN

CH2

NCu

2+ SO42-

P CH2

CH2

N

COO

CH2

COO

Cu

P COO

P COO

Cu

Lewatit TP220: Bispicolylamine-Resin

Lewatit TP207: IDA-Resin

Lewatit CNP 80: WAC-Resin

+ NH3

+ NH3

+ NH3

?

?

?



Comparison of differentResin Types: Break Through Curves

Vergleich(Ohne Salz)

0

50

100

150

200

250

0 100 200 300 400 500

BV

NH4+

/ppm

NH4+(mg/L)CNP-80 NH4+(ppm)TP207 NH4+(ppm)TP220

NH3 feed concentraiton Operating Conditions: SV= 10 BV/h, resin Cu-doped with 10 BV of 50 g/L CuSO4*7H20 soln. + 5 BV of rinse with demin water Cu-doping rate: CNP80:70 g/L TP207: 55 g/L TP220: 41 g/L feed solution: demin water + 200 ppm NH3, pH = 10.5

Curve measured with demin water - background

Only CNP80 (WAC) and TP207 (chelating resin) work


Vergleich(mit Salz)

0

50

100

150

200

250

0 100 200 300 400 500

BV

NH4+

/ppm

NH4+(TP207)/ppm NH4+(CNP-80)/ppm

Operating Conditions: SV= 10 BV/h, resin Cu-doped with 10 BV of 50 g/L CuSO4*7H20 soln. + 5 BV of rinse with demin water Cu-doping rate: CNP80:70 g/L (1.1 mol/L) TP207: 55 g/L (0.86 mol/L) feed solution: 1 g/L salt: NaCl(80% p.w and CaCl2 20% p.w.) + 200 ppm NH3, pH = 10.5


Comparison of differentResin Types: Break Through Curves

Only CNP80 (WAC) works with salt background

NH3 feed concentraiton

Curve measured with salt containing water - background



Effect of Salt-Content in Background On NH4-Uptake

0

50

100

150

200

250

0 100 200 300 400 500

BV

NH4+

/ppm

NH3 feed concentraiton

0 g/L salt

1 g/L salt

1,7 mg/L salt

5 g/L salt

Increasing salt content makes NH3 uptake decrease

Operating Conditions: SV= 10 BV/h, resin Cu-doped with 10 BV of 50 g/L CuSO4*7H20 soln. + 5 BV of rinse with demin water Cu-doping rate: CNP80:70 g/L feed solution: various salt concentrations: NaCl 80% p.w and CaCl2 20% p.w. + 200 ppm NH3, pH = 10.5


0

50

100

150

200

250

0 50 100 150 200 250

BV

NH4+

(Cu2

+)/p

pm

0

2

4

6

8

10

12

pH-W

ert

NH4+(ppm) Cu2+(ppm) pH-Wert

0

50

100

150

200

0 100 200 300 400 500

BV

NH4+

(Cu2

+)/p

pm

0

2

4

6

8

10

12

pH-W

ert

NH4+/ppm Cu2+/ppm pH-Wert

Operating Conditions: SV= 10 BV/h, resin Cu-doped with 10 BV of 50 g/L CuSO4*7H20 soln. + 5 BV of rinse with demin water, Cu-doping rate: CNP80:70 g/L, TP207 55 g/L, feed solution: 1 g/L total salt content (NaCl 80% p.w and CaCl2 20% p.w.) + 200 ppm NH3, pH = 10.5

TP207 CNP 80

TP207 leaches high concentrations of copper at the beginning, CNP 80 shows extraordinarily low leakage over the whole cycle

< 0.5 mg/L Cu2+

TP207 drops pH in outlet, CNP80 keeps pH in outlet neutral


Cu2+-leakage and pH in outlet of column



NH3-uptake as a function of NH3 feed concentration

020406080

100120140160180200

0 200 400 600 800

BV

NH

4+/p

pm

NH4+ mit ca 200ppm NH4+ mit ca 100ppm

Feed concentration = 200 mg/L NH3

Feed concentration = 100 mg/L NH3

Operating Conditions: SV= 10 BV/h, resin Cu-doped with 10 BV of 50 g/L CuSO4*7H20 soln. + 5 BV of rinse with demin water, Cu-doping rate: CNP80:70 g/L, feed solution: just demin water + 200 ppm NH3, pH = 10.5

equilibrium capacity around 50 g/L NH3

(2.9 mol/L )

equilibrium capacity around 40 g/L NH3 (2.3 mol/L)



Regeneration

List of Potential Regeneration Methods*:

•Acid

•Salt

•Salt+Acid

•Steam

•Vacuum

*) All methods worked in orienting tests to remove the NH3 from the resin, but the difficulty is to thereby keep as much Cu2+ on the resin as possible



Regeneration with sulfuric acid

pH, NH3, Cu2+

Acid

NH3-loaded resin

3 BV of water

pH, NH3, Cu2+

Acid

NH3-loaded resin

3 BV of water

Operating Conditions: 100 ml resin, 300 ml of eluate, original Cu2+ load on resin: 70 g/L, original NH3 load on resin: 36 g/L, concentration of H2SO4 98%, H2SO4 consumption 5 ml, ….

Concentration of NH3 and Cu2+ in Eluate

0123456789

0 2 4 6 8

pH-Wert

NH4+

(g/L

)

0

100

200

300

400

500

600

Cu2+

/ppm

NH4+(g/L) Cu2+(mg/L)




0

10

20

30

40

50

60

70

0 2 4 6 8

pH-Wert

NH4+

/%

00,511,522,533,544,55

Cu2+

/%

NH4+/% Cu2+/%

Elution Grade:

65% elution of NH4 with at the same time only 1.5% of loss of Cu2+ doping is a quite good result


0

20

40

60

80

100

120

0 100 200 300 400 500 600

BV

NH

4+/p

pm



first cycle

second cycle

Breakthrough curves before and after first regeneration:

Regeneration works in principle ! Operating capacity suffers around 10% from regeneration

Operating Conditions: SV= 10 BV/h, resin Cu-doped with 10 BV of 50 g/L CuSO4*7H20 soln. + 5 BV of rinse with demin water, Cu-doping rate: CNP80:70 g/L, feed solution: just demin water + 100 ppm NH4

+, pH = 10.5


Summary

Selective NH3 removal from water proofed principally feasible

WAC resin (CNP80) surprisingly worked much better than chelating resins TP207 and TP220(in terms of NH3, uptake, influence of salt, Cu-release from the resin)

Nearly no copper leakage with CNP80 (!?), Cu2+ < 0.5 ppm!

Increasing salt content in feed solution decreasesNH3 uptake

NH3 equilibrium capacities of up to 50 g/L of NH3 found(each Cu2+ binds 2…3 molekules of NH3)

NH3 removal from resin principally possible by acid, salt, steam, vacuum

XX

X

X

X

X

Σ=… X Very low leakag of NH3 (99% removal rate in the beginning)



Open Questions

Kinetics seem to be slow! Influence of flow rate on operating capacity ?

Influence of pH on NH3 uptake? Would the process work at pH=7

How to adapt process to potable water requirements?

Over all efficiency of a technical process?

?

???

?

Operating capacities after third and further regeneration ?

?

Why does a selective resin leache more copper than a non selective resin?

? Can the regeneration method be further optimized ?

?

Benchmark with competing process such as Clinoptiloite-Adsorption or air stripping?



Application Status

Process still to be regarded as a „Process in Development“

!

!

No reference plants existing jet. Pilot tests with real waste water should be started!

!Process so far seems only applicable for waste water / ground water treatment. For potable water the process does not seem applicabpe due to required pH setting (operating pH = 10)

! First results are looking very promising regarding feasibility of this new process approach !

Summary


Summary- New interesting selective ion exchange processes can be realized by doping ion exchange resins with metal ions

- As an example the latest results of process development studies regarding the selective removal of F- and NH3 were presented

- Both processes look very promising to be technically meaningful but further development work has to be carried out to make them “safe to apply”

- Surprising effects were found e.g.:

- increasing F- uptake with increasing salt background

- lower dumping of Cu2+ with non-chelating resin

- etc.

Thank you very muchfor your attention.


Disclaimer

This information and our technical advice – whether verbal, in writing or by way of trials – are given in good faith but without warranty, and this also applies where proprietary rights of third parties are involved. Our advice does not release you from the obligation to check ist validity and to test our products as to their suitability for the intended processes and uses. The application, use and processing of our products and the products manufactured by you on the basis of our technical advice are beyond our control and, therefore, entirely your own responsibility. Our products are sold in accordance with the current version of our General Conditions of Sale and Delivery.

LEWATIT® and IONAC® are registered trademarks of LANXESS AG

31 new interesting applications for ccp_sw tes seminar

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