c.i.e. srl - pural® process

PURAL℗ PROCESS

Technology to remove Sulphates, by Anodizing rinses

for final dumping as : ♦ irrigation water quality

or for ♦ partial or total reuse (Z.L.D.) by Franco FALCONE

C.I.E. General manager

ALUMINIUM TWO THOWSEND INTERNATIONAL CONGRESS – Milano Room Smeraldo - 05/15/2013, h. 12:00 am

ANODIZING LINE

Reuse

WASTE

PURAL PLANT

or Irrigation

COMPAGNIA ITALIANA ECOLOGIA S.R.L.

2011 - CIE’S 30TH ANNIVERSARY CRUISE

♦ CIE foundation: 1981

32 years of expertise

in Water Treatment for

Metal Finishing Lines


APPLIANCES Aluminium Wheels

COIL COATING ALUMINIUM EXTRUSIONS

ALUMINIUM CANS

WASTE WATER PLANTS SPECIFICALLY DEDICATED TO METAL FINISHING LINE

TARGET MARKET: METAL FINISHING INDUSTRIES

AUTOMOTIVE

COMPAGNIA ITALIANA ECOLOGIA S.R.L. INNOVATIONS AWARDS & PATENTS

Die Cleaning

Bath Dirty Dies

NaOH

Neutralization

& Regeneration

SOLIDS

Al(OH)3 CaCO3

CATALYTIC PROCESS FOR CAUSTIC SODA RECOVERING

BY SPENT DIE CLEANING SOLUTION

Patent n°1398512

Regenerated NaOH

PROCESS FOR MINIMIZE SULPHATES AND FLUORIDES

GENERATING ‘IRRIGATION’ AND REUSABLE WATER

ANODIZING LINE

PURAL PLANT

WASTE

Reuse or

Irrigation

COMPAGNIA ITALIANA ECOLOGIA S.R.L. WORLDWIDE CIE CUSTOMERS

COMPAGNIA ITALIANA ECOLOGIA S.R.L. ACTIVITIES FOR ALUMINIUM LINES

1) REVERSE OSMOSIS UNITS

2) DEIONIZING AND MIXED BED UNITS

3) CHEMICAL DOSING AND CONTROLLING UNITS

4) WASTE WATER PLANTS (PURAL® TECHNOLOGY)

5) ZERO LIQUID DISCHARGE PLANT

6) TELESERVICE AND TELEASSISTANCE


• European limits for dumping in sewers:

• Sulphates (𝑆𝑂4=)

• Fluorides (𝐹−)

≤ 1000 ppm

≤ 10 ppm

• Local authorities may require to drop this limits till:

≤ 500 or 300 ppm

≤ 6 or 4 ppm


• Fluorides (𝐹−)

POLLUTING LIMITS FOR WASTE WATER

• Main polluting agents of water :

• Aluminium (𝐴𝑙)


• Fluorides (𝐹−) (for painting lines)


Use special Additives( PURAL F10) • Fluorides (𝐹−):

• Sulphates (𝑆𝑂4=) ≤ 1000 ppm:

• Sulphates (𝑆𝑂4=) ≤ 300 ppm:

Use of greatest volume of water than necessary

Not achieved except strong dilution

LIMITS RESPECT APPROACH

SOLUTION : Use specific technology such PURAL®

COMPAGNIA ITALIANA ECOLOGIA S.R.L. MODERN RINSING MANAGEMENT PERFORMANCES

• DOUBLE OR TRIPLE CASCADE BACK RINSES

• DROPPING AND CARRY-OVER MINIMIZING

• INSTRUMENTAL MANAGING BY CONDUCTIVITY

GOAL: REDUCE WATER CONSUMPTION •

EFFECT: SULPHATES OVERCOME LIMITS •

SOLUTION: Use specific technology such as PURAL®

COMPAGNIA ITALIANA ECOLOGIA S.R.L. DIFFERENTS CONDITIONS OF WATERS FROM ANODIZING

• Natural neutralization: of NaOH and H2SO4 used in workshop

2NaOH + H2SO4 → Na2SO4 (pH = 7)

Balance: 80 Kg of NaOH100% = 100 Kg of H2SO4 98%

- STANDARD ANODIZING LINE:

• Satinized ≤ 80% of production:

• Satinized ≥ 80% of production:

(NaOH or Ca(OH)2) CAUSTIC for neutralization needs

ACID for neutralization needs

- ANODIZING LINE EQUIPPED WITH OXIPUR (ACID RECOVERY UNIT)

• Satinized ≤ 50% of production:

• Satinized ≥ 50% of production:

(NaOH or Ca(OH)2) CAUSTIC for neutralization needs

ACID for neutralization needs

COMPAGNIA ITALIANA ECOLOGIA S.R.L. CURRENT PURIFICATION TECHNOLOGY

• NaOH neutralization : H2SO4 + 2NaOH → Na2SO4 (Totally soluble)

• Lime neutralization : H2SO4 + 2Ca(OH)2 → CaSO4

Results: Sulphates totally

Results: Sulphates

NOT REMOVED

PARTIALLY REMOVED

Results: IMPRACTICABLE FOR DRAMMATIC COSTS AND SLUDGES GENERATION

• Barium neutralization : H2SO4 + 2Ba (OH)2 → BaSO4

COMPAGNIA ITALIANA ECOLOGIA S.R.L. PURAL® TECHNOLOGY

• PURAL IS THE ONLY AVAILABLE TECHNOLOGY TO PRECIPITATE:

OVER THAN 95% OF SULPHATES

SO4= ARE PRECIPITATED AS TOTALLY INSOLUBLE COMPLEX:

CaO.Al2O3.CaSO4.H2O (Ettringite)

CaO.Al2O3.CaF2.H2O (Pseudo- Ettringite)

• NOTE: PURAL IS SUITABLE ALSO FOR FLUORIDES PRECIPITATION (PAINTING LINES)

COMPAGNIA ITALIANA ECOLOGIA S.R.L. PURAL® RESULTS

• Al ≤ 0,5 ppm • SO4

= ≤ 150 ppm • F- ≤ 4 ppm • CO3 ≥ 200 ppm • Hardness ≤ 40°F • Conductivity ≤ 400 μS

ANALYTICAL VALUES OF PURIFIED WATER ARE FANTASTIC:

- WATER TREATED WITH PURAL CAN BE:

• DUMPED RESPECTING ANY KIND OF LOCAL REGULATION • USED FOR ‘IRRIGATION’ • SENT BACK TO ALKALINE SECTION

PURAL REDUCE WATER CONSUMPTION OF 50% AND IS THUS STRATEGIC TO GAIN A

ZERO LIQUID DISCHARGE (ZLD) PLANT.

COMPAGNIA ITALIANA ECOLOGIA S.R.L. PURAL® TECHNOLOGY

STAGE 1: USE OF A COMBINATION OF LIME AND AN

ADDITIVE (PURAL 03S) FOLLOWED BY CLASSIC

FLOCCULATION AND SETTLING SECTION.

STAGE 2: NEUTRALIZATION WITH 𝑪𝑶𝟐 TO ELIMINATE THE

EXCESS OF CALCIUM, FOLLOWED BY A SECOND

SETTLING.

PURAL PROCESS IS REALIZED IN TWO STAGES:

COMPAGNIA ITALIANA ECOLOGIA S.R.L. PURAL® TECHNOLOGY ON ANODIZING

Flocculation

pH control

Sludge Thickener

PURAL treatment

USE

FO

R

IRR

IGA

TIO

N

PURAL neutralization tank

pH control

LAMELLA SETTLER

Charcoal Filter

Sand Filter

Filter Press

LAMELLA SETTLER Retaking

tank

Ca(OH)2

PURAL 03S FLOCC. CO2

REUSE TO ANODIZING

LINE

SUITABLE FOR…..

WATER QUALITY ● SO4

= < 150 mg/l ● Al 3+ < 0,5 mg/l ● Cond ≤ 400 µS

WASTE WATER FROM ANODIZING LINE

PURAL® FLOW CHART

ALKALINE CLEANING

ALKALINE ETCHING

RINSE

RINSE 2

RINSE 3

ACID DESMUTTING

RINSE

ANODIZING

RINSE 3

ELECTROCOLOR

RINSE

D.I. RINSE

SEALING

RINSE 1

D.I.

UNIT

RINSE 2

RINSE 1

OXIPUR

PURAL®

process

COMPAGNIA ITALIANA ECOLOGIA S.R.L. PURAL® APPLICATION TO ANODIZING LINE

USEBLE FOR IRRIGATION

FRESH WATER

WATER QUALITY ● SO4

= < 150 mg/l ● Al 3+ < 0,5 mg/l ● Cond ≤ 400 µS FINAL PURIFICATION

PLANT

neutralization by CO2

COATING LINE

ALKALINE CLEANING

ALKALINE ETCHING

RINSE

RINSE 2

RINSE 3

ACID DESMUTTING

RINSE

ANODIZING

RINSE 3

ELECTROCOLOR

RINSE

RINSE 1

D.I. RINSE

SEALING

D.I.

UNIT

RINSE 2

RINSE 1

ANODIZING LINE

ALKALINE ETCHING

RINSE 2

RINSE 1

ACID DEOXIDIZING

RINSE 2

RINSE 1

CROMATING or CR FREE

RINSE 2

RINSE 1

OXIPUR


FINAL PURIFICATION PLANT

(neutralization by CO2

USABLE FOR IRRIGATION

PURAL®

process

PREPURIFIED WATER

FRESH WATER

PURAL® FOR ANODIZING + COATING LINE

FRESH WATER

COMPAGNIA ITALIANA ECOLOGIA S.R.L. ZERO LIQUID DISCHARGE

• PURAL® TECHNOLOGY IS PROPAEDEUTIC TO ZLD

• Water coming from PURAL, after a dedicated Sand + Charcoal

Filter are sent to a special High Pressure Reverse Osmosis Unit (H.P.R.O.)

• H.P.R.O. Generates two flow :

- 80-90% of low salinity water (PERMEATE)

- 10-20% of high salinity water (REJECT)

PERMEATE is sent directly to reuse

REJECT is sent to a Multiple Effect Evaporator

ACID

DESMUTTING

COMPAGNIA ITALIANA ECOLOGIA S.R.L. ZERO LIQUID DISCHARGE FOR ANODIZING LINE

Flocculation

pH control

Sludge Thickener

PURAL treatment

RINSE

PURAL neutralization tank

pH control

LAMELLA SETTLER

Filter Press

LAMELLA SETTLER

Ca(OH)2

PURAL 03S FLOCC. CO2

ANODIZING

RINSE 1

RINSE 2

RINSE 3 ELECTROCOL

OR RINSE

ALKALINE

CLEANING RINSE

ALKALINE

ETCHING RINSE 1

RINSE 2

RINSE 3

Retaking tank

REJECT

PERMEATE

Evaporator

DIS

TIL

LA

TE

High Pressure Reverse Osmosis Neutralizi

ng

By CO2 or

HCl

COMPAGNIA ITALIANA ECOLOGIA S.R.L. OPERATING COSTS COMPARISON

COST/SQM OF ANODIZED SURFACE:

9,1 cent/m2

€ 0,00

€ 5,00

€ 10,00

€ 15,00

€ 20,00

€ 25,00

€ 30,00

€ f

or

1 h

ou

r

PURAL®

H2O

Lime+Pural 03


11,3 cent/m2

€ 0,00

€ 5,00

€ 10,00

€ 15,00

€ 20,00

€ 25,00

€ 30,00

€ f

or

1 h

ou

r

Z.L.D.

Lime+Pural 03

Energy

€ 0,00

€ 5,00

€ 10,00

€ 15,00

€ 20,00

€ 25,00

€ 30,00

€ f

or

1 h

ou

r

TRADITIONAL

H2O

Lime


10,6 cent/m2

COMPAGNIA ITALIANA ECOLOGIA S.R.L. APPLICATION FOR ZLD: CASE HISTORY

750 m3/day

Aluminium Melting

Aluminium Rolling

Aluminium Coil Coating

• Total of water recycled:

• Waste water source:

- GREECE

Leading company for Aluminium production (250.000 ton/years)

- pH 7,5

- 𝑨𝒍 ≤ 1 ppm

- 𝑺𝑶𝟒= ≤ 150 ppm

- 𝑭− ≤ 4 ppm

- Conductivity ≤ 400 μS

• Quality of recovered water:

Z.L.D. 750 m³/day ZERO LIQUID DISCHARGE


PURAL (FLUORIDE /SULPHATES/ COD

REMOVAL)

DISINFECTION

SAND

FILTER

CHARCOAL

FILTER

ULTRA

FILTRATION.

ELVAL

WORKSHOP

COIL COATING LINE

FOUNDRY

ROLLING MILLS

COOLING TOWER

DISTILLED

WATER

TO R

EUSE

TO

ZLD

HIGH PRESSURE REVERSE OSMOSIS

DEOLING

UNIT

PERMEATE

CRYSTALYZER

MULTI EFFECT

EVAPORATOR

(3 STAGE)

REJECT

SLUDGES & SOLIDS


ZLD – PURAL: SULPHATES/FLUORIDES TREATMENT

APPLICATION FOR ZLD: CASE HISTORY


ZLD – PURAL 03 STORAGE AND DOSING



ZLD – PURAL: LAMELLA GRAVITY SETTLER



ZLD – MULTI MEDIA FILTERS



ZLD – CHARCOAL FILTERS



ZLD – U.F. DOUBLE UNIT



ZLD – REVERSE OSMOSIS AND NANO FILTRATION



ZLD – MULTIPLE EFFECT EVAPORATOR



ZLD – GENERAL VIEW

COMPAGNIA ITALIANA ECOLOGIA S.R.L. OTHER FIELD OF APPLICATION

• STEEL AND STAINLESS STEEL PICKLING

• COPPER/BRASS PICKLING AND BRIGHTENING

• GALVANIZING AND ELECTROGALVANIZING LINE (FOR PICKLING SECTION)

• STEEL COLD FORMING: PICKLING AND PHOSPHATING LINES OF TUBES,

BARS, WIRE, BOLTS AND SCREWS

PURAL® PROCESS CAN BE SUCCESSFULLY APPLIED ALSO ON:

Wherever Sulphates and Fluorides solubility violate final water limits, PURAL® is the only

convenient solution

COMPAGNIA ITALIANA ECOLOGIA S.R.L. CONCLUSIONS

PURAL® IS THE SOLUTION TO REACH MANY GOALS:

• PRODUCE WATER RESPECTING ‘LOW’ SULPHATES, FLUORIDES LIMITS

• PRODUCE WATER SUITABLE FOR IRRIGATION

• PRODUCE A FULL REUSABLE WATER FOR ALKALINE RINSING

• REDUCE DRASTICALLY WATER CONSUMPTION (50%)

• COMPARABLE OPERATING COSTS WITH TRADITIONAL W.W.T.P.

• 50% REDUCTION OF COSTS FOR WATER SAVING

• BASIC TECHNOLOGY FOR ZERO LIQUID DISCHARGE

c.i.e. srl - pural® process

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