INTERNATIONAL AND INDIAN CASE STUDIES ON ZLDSTUDIES ON ZLD

Leif Ramm-Schmidt, Ramm-Schmidt Consulting Ltd, Finlandrepresenting Arvind Envisol Private Limited Ahmedabad Indiarepresenting Arvind Envisol Private Limited, Ahmedabad, IndiaPresented at: Seminar and Training Workshop on Zero Liquid Discharge, Ahmedabad 28th January 2014

WORD TRENDS

• Environmental pressure from population growth• Environmental pressure from population growth• Clean water reservoirs steadily diminishing• Growing demand for all kinds of water purification• Growing demand for all kinds of water purification• In industry in particular:

Water recovery– Water recovery– Closing of water loops

N t h l• New technology:– Low cost corrosion resistant polymeric heat

exchangersexchangers– To be used in highly efficient evaporation

technology

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technology

WHY IS ZERO DISCHARGE NEEDED IN INDUSTRY ?

• Industry uses huge volumes of pure water d i j ll t f tand is a major polluter of water courses

• Conventional effluent treatment does not remove pollutants sufficiently nutrients andremove pollutants sufficiently – nutrients and salts are not well separated, recycle of water not possiblenot possible

Typically:

ZZ di hdi h f tf tZero Zero discharge discharge rere--use of wateruse of water

Leaving the clean water for human consumption - with great improvement in standard of living

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g g

POLLUTION OF RIVERS AND WATERS

Man made eutrophication

Industry plays a majorrole

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POLLUTION OF RIVERS AND WATERS

Death of ecosystem,y ,diseases spread, no source for drinking waterwater......

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TECHNOLOGIES IN EFFLUENT TREATMENTTECHNOLOGIES IN EFFLUENT TREATMENT

Adsorption (e g activated carbon)Adsorption (e.g. activated carbon)Ion exchange and EDIChemical precipitationMembrane technologies Methods have Membrane technologies

Ultrafiltration (UF)Nanofiltration (NF)Reverse osmosis (RO)

Methods have often to be combined for ( )

ElectrodialysisEvaporationDistillation

m fzero discharge operation or to

d h FlotationAir/steam strippingElectrical methods

meet discharge limits

ElectrolyseElectro coagulation

Biological treatment

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POLLUTANTS TO REMOVEPOLLUTANTS TO REMOVE

Dissolved substances:Cations (e.g. heavy metals)• Monovalent ions• Multivalent ions• Complexed ions• Complexed ions• Ammonium (NH4

+)

Anions• Monovalent (e g chloride)• Monovalent (e.g. chloride)• Multivalent (e.g. SO4

2-)

Organic compounds• Carbohydrates• Carbohydrates• Proteins• Alcohols• Solvents (e.g. hydrocarbons)• Pigments• Pigments• Pesticides

COD in general (= indicator of any oxidizable matter)

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PRIMARY RULE IN ZERO DISCHARGEPRIMARY RULE IN ZERO DISCHARGE

• Zero discharge with water re-cycle will work only if y yall pollutants and salts are almost 100% removed.

• If not, accumulation of ,salts in the process will take place!p

Evaporation and RO are only technologies that remove dissolved salts

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remove dissolved salts

EVAPORATION - THE METHOD TO ACCOMPLISH TOTALLY CLOSED WATER LOOPTOTALLY CLOSED WATER LOOP

PROCESSPROCESSMAKE-UP WATER

PROCESSPROCESS

WASTE WATERWASTE WATERFRESH WATERFRESH WATER

T bli• To public sewer• Treated locally to meet

discharge limitsInternal measures taken to use water efficientl • Discharged to natureefficiently

PURGED SOLIDS

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EVAPORATIONEVAPORATION

WHY EVAPORATION ?

From a technological point of view evaporation is an ideal method for purification of industrial peffluents, process waters and landfill leachates for the following reasons:

• All non-volatile substances can be completely completely separatedseparated

• Water recovered from the effluent stream is of high qualityhigh quality

• Evaporated water (distillate) can, as such, in most cases be reusedreused in process or discharged into the

tnature• Harmful solids can be concentratedconcentrated to a

manageable amount for appropriate disposal

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manageable amount for appropriate disposal• Valuable solids can be recoveredrecovered and reused

NEW POLYMERIC FILM EVAPORATION TECHNOLOGY 1

Q = U x A x DT Low cost Evaporative surface o large heat transfer surfaceo small temperature difference

Q = U x A x DTPFan = C x MF x DT

o small temperature differenceo low energy use - typically 8 to 14 kWh per m3 of

purified water

Efficient production of polymeric heat exchangerl b helements by new machine

(1,5 million m2/year)

C t l f ti f Costs only a fraction of metallic ones

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NEW POLYMERIC FILM EVAPORATION TECHNOLOGY 2

Polymeric surface Polymeric surface corrosion resistant less scaling flexible - easy cleaningflexible easy cleaning

Mechanical Vapor RecompressionPrinciple (MVR) minim l st m r c lin minimal steam or cooling

water required

Simplified Vapor Compressor p p p(Fan) Design low operating speeds reliable easy maintenance

Also multi-effect (ME) systems using waste heat or solar

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MVR EVAPORATOR - OPERATIONMVR EVAPORATOR OPERATION

Low speed vapori fFan blower as vapor compressor

Compressed vaporImpellerVacuumvessel

compression fan

Condensati oninner surface

Fan blower as vapor compressor

por

et

inner surfaceFalling filmevaporatio nouter surface

Va inle

Vacuu mpump

Condensa teCirculationwater

Condensate tank

Feed efflue nt

Concentrate

water

Polymeric Cartridges

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y g

CASE STUDIES ON ZLDCASE STUDIES ON ZLD

1 C d f t i C d1. Copper rod manufacturing, Canada2. Recycle paper manufacturing, Saudi Arabia3 P l S d3. Paper plant, Sweden4. Landfill leachate treatment, Finland5. Aluminum chromating process, Finland6. Textile dyeing industry 1, India7. Textile dyeing industry 2, India8. Bottle washing plant, India9. Flue gas condensate cleaning, Finland

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TYPICAL APPLICATION AREASTYPICAL APPLICATION AREAS

Textile industry Textile industry Steel and metal industry Mining industry Mining industry Pulp & Paper Food and feed industry Landfill leachate Groundwater remediation Seawater desalination Seawater desalination Chemical industry Electronic industryE y Power plants Pharma industry

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COPPER ROD MANUFACTURING RINSING WATER TREATMENT – DILUTE SULFURIC ACID, CANADA AND FRANCEDILUTE SULFURIC ACID, CANADA AND FRANCE

P d Procedure: Pickling of rod with H2SO4

Ri i f d b t Rinsing of rod by water MVR evaporation of effluent, return

of condensate to rinsing bathof condensate to rinsing bath Final concentration of effluent Electrolysis recovery of copper and H SO Electrolysis, recovery of copper and H2SO4

Return of H2SO4 to process Return of pure copper to process Return of pure copper to process

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Plant capacity 350 KLD

COPPER ROD MANUFACTURING RINSING WATER TREATMENT – DILUTE SULFURIC ACIDTREATMENT – DILUTE SULFURIC ACID

Pickling

Copper Rod

Protection BasinRinsing

H SO2 4 Surfactant

Vapor

Recovery ofWater

350 KLDCondensate

Concentrate Electro-

Evaporator360 / 24L-1.2

Copper

Acid350 KLD

Steam

Boiler Stripper

winning Copper

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CuAcid

CONTINUOUS SURFACE TREATMENT OF COPPER ROD CANADACOPPER ROD, CANADA

P t U it F d C t t C d tParameter Unit Feed Concentrate Condensate

Conductivity µS/cm < 100pH ~1.5 < 1 > 3.5pH 1.5 1 3.5SO4 mg/l 1 450 69 500 < 14Copper mg/l 600 29 400 < 3TDS mg/l 2 100 100 000 < 50TDS mg/l 2 100 100 000 < 50

Clean water recovery 98%

P tiPower consumption: 12 kWh/m3 clean water

COPPER ROD, BENEFITS OF EVAPORATION

Before With Evaporator Process water Ground water + RO Not needed

Reactive Physico chemical treatment Not neededReactive compounds

Physico-chemical treatment (lime…)

Not needed

Treatment of the precipitate

Filter press Not needed

Reject Decantation Not needed

Before With Evaporator Recovery of copper Impossible Electrolysis (existing) Recovery of the acid Impossible Recycle to the pickling y p y p g

bath Recycling of the process water

Impossible Condensate (98%)

COMMENT BY OWNER

"Th l ti i"The low energy consumption is spectacular and real. Thanks to this system, we've decreased overall factory energy consumption, while increasingenergy consumption, while increasing our production rate and our product quality " ( C )quality. (André Claude Lessard)

Plant has been in continuous operation since year 2000

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since year 2000

RECYCLE PAPER MILL WATER TREATMENT, SAUDI ARABIAARABIA

P d Procedure: Flotation of raw waste water for

fiber removalfiber removal Sand filtration MVR evaporation of effluent return of MVR evaporation of effluent, return of

condensate to process after pH control Concentrate transported by truck Concentrate transported by truck

to solar drying pond Make up water from ground well p g

(high TDS water), softened by evaporation

Plant capacity 2 x 600 KLD water recovery > 90%

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Plant capacity 2 x 600 KLD, water recovery > 90%Power consumption 10 kWh/m3 clean water

SET-UP OF RECYCLE PAPER MILL WATER TREATMENT PLANT SAUDI ARABIATREATMENT PLANT, SAUDI ARABIA

600 KLD

600 KLDReturn to process

1/31/2014Achema 2000 - Water Treatment and Recycling

RECYCLE PAPER MILL SAUDI ARABIARECYCLE PAPER MILL, SAUDI ARABIA

EVAPORATION AS KIDNEY IN A PAPER MILLEVAPORATION AS KIDNEY IN A PAPER MILL

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LANDFILL, FINLAND - LEACHATE TREATMENT

Procedure: Procedure: Collection of leachate water in wells

in landfill, pumping to basinp p g Sand filtration Acidification to pH 4 to break p

down CaCO3

CO2 removal by air stripper MVR evaporation of effluent,

condensate to nature after pH adjustment (pH 7) Concentrate pumped back to remote

part of landfill after pH adjustment (pH 7)

25Plant capacity 120 KLD

Achema 2000 - Water Treatment and Recycling

LANDFILL, FINLAND - LEACHATE TREATMENT Fan

Vacuum pump

HeatExchangers

Circulation Water Condensate, pH 7Circulation Water Condensate, pH 7

Concentrate, pH 7

CO

Feed Water, pH 7

Fan

CO2

pH 4

Leachate

NaOHCO - Removal Column

2Filter

Basin Acid

1/31/2014Achema 2000 - Water Treatment and Recycling

LANDFILL, FINLAND,

120 KLD120 KLD

ALUMINUM PROFILE CHROMATE TREATMENT -CLOSED WATER LOOP CONCEPT CLOSED WATER LOOP CONCEPT

Procedure: Procedure: Surface treatment of aluminum components

with chromium, rising in between stepsg p Flocculation of rinsing water to remove

aluminum, filtration MVR evaporation of rinsing water, return of condensate to rinsing bathsFl l f h Flocculation of chromium

Chromium sludge and concentrate to Hazardous waste plant

Plant capacity 50 KLD

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Plant capacity 50 KLD

Achema 2000 - Water Treatment and Recycling

ALUMINUM PROFILE CHROMATE TREATMENT -CLOSED WATER LOOP CONCEPT

ing

xidi

zatio

n

ing

omat

engin

g

ing

line

ing

line

easi

ng

AcidBaseFlocculation

Rin

si

Deo

x

Rin

si

Chr

oco

ati

Rin

s i

Rin

si

Alk

alpi

ckli

Alk

alde

gre

> 99%AcidFlocculant

Settling Tank

FiltrationCondensate

pH 5-7< 10 S/ cmm

> 99% water recovery

Al deposit ConcentratepH 3-6

< 50 000 S/ cmm

Evaporation ratio up to 1:500Evaporator

Feed Condensate

Concentrated SaltsConcentrate

Municipal Waste Water Hazardous Waste Settling Tank Cr depositTreatment Plant Disposal Plant

ARVIND SANTEJ TEXTILE DYEING - CLOSED WATER LOOP CONCEPT INDIALOOP CONCEPT, INDIA

Procedure: Procedure: Process: Bleaching, Neutralising, Washing, Primary Clarifier,

Secondary Clarifier, Flocculator, Fixing &Softeningy g g Sand filter to trap suspended solids Pre-concentration in RO, recycle of water to processy p Reject to MVR evaporation, recycle of condensate to process Concentrate to FC-crystallization, recycle of condensate to y y

process Recovery of salts in centrifuge

Plant capacity 3 x 200 KLD

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Plant capacity 3 x 200 KLDIn operation since 2011

ARVIND SANTEJ TEXTILE DYEING - CLOSED WATER ARVIND SANTEJ TEXTILE DYEING CLOSED WATER LOOP CONCEPT, INDIAWATER BALANCE

Number refers to relative flow %

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Number refers to relative flow %

Sand filter RO MVRFrom process

100 90100 3

FC

7SludgeConcentrate

FC crystallizator

Clean water to process2

99 Concentrate

CentrifugeSalt

99 Concentrate

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TYPICAL CONCENTRATOR/CRYSTALLIZATORTYPICAL CONCENTRATOR/CRYSTALLIZATOR

Centrifuge

Salt

32Concentrator/crystallizator

ARVIND SANTEJ TEXTILE DYEING

Parameter Unit RO feed Evaporator feed (MVR)

Condensate Concentrate

pH 6-10 6 - 7 6 - 7 7-7 5p 6 10 6 7 7 7,5

Temperature oC 35 - 45 35 - 45 45 - 55 50 - 55

TDS mg/l 3.000 – 30.000 – 40.000 < 150 90.000 -120.0004.000

BOD mg/l 300 - 500

COD mg/l 1.000 -1.500mg/l 1.000 1.500

Total Hardness

mg/l 500

RO-recovery 90%RO recovery 90%Evaporator (MVR) recovery 70%

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BOMBAY RAYON TEXTILE DYEING - CLOSED WATER LOOP CONCEPT BANGALORE INDIALOOP CONCEPT, BANGALORE, INDIA

Process: Process: Bleaching, Neutralising, Washing, Dyeing, Acid washing, Washing, Soaping, Hot washing, Fixing & Softening.

Effluent: Sand filter to trap suspended solids Pre-concentration in RO, recycle of water to process Reject to MVR evaporation, recycle of condensate to process Concentrate to ME evaporator for final concentration, recycle of

condensate to process Concentrate to solar drying pond

Plant capacity 3 x 500 KLD

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Plant capacity 3 x 500 KLDIn operation since year 2006

BOMBAY RAYON 3 X 500 KLD

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BOMBAY RAYON 3 X 500 KLD

Sample bottlesSample bottles

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BOMBAY RAYON TEXTILE DYEING - CLOSED WATER BOMBAY RAYON TEXTILE DYEING CLOSED WATER LOOP CONCEPT, INDIAWATER BALANCE

Number refers to relative flow %

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Number refers to relative flow %

Sand filter RO MVRFrom process

100 85100 4

ME

11SludgeConcentrate

ME evaporator

Clean water to process2

98 Concentrate

Solar pond

98 Concentrate

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BOMBAY RAYON TEXTILE DYEINGBOMBAY RAYON TEXTILE DYEINGANALYSIS

Parameter Unit RO feed Evaporator feed (MVR)

Condensate Concentrate

pH 6 - 10 6 - 7 7 – 7,5 7 - 7 5p 6 10 7 7,5 7 7,5

Temperature oC 35 - 45 35 - 45 45 - 55 50 - 55

TDS mg/l 3.000 – 25.000 – 30.000 < 125 100.000 -4.000 120.000

BOD mg/l 300 - 500

COD mg/l 1.000 -1.500mg/l 1.000 1.500

Total Hardness

mg/l 200

RO-recovery 85%Evaporator (MVR) recovery 75%

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HINDUSTAN COCA COLA - CLOSED WATER LOOP CONCEPT GOBLEJ INDIACONCEPT, GOBLEJ, INDIA

Process: Process: Bottle washing, NaOH, several steps, final rinsing, neutralization

Effluent: Aerobic bio-treatment, settling, sludge treatment MBR (Membrane Bio Reactor)( ) Pre-concentration in RO, recycle of water to process Reject to MVR evaporation, recycle of condensate to process j p y p Concentrate to FC-crystallization,

recycle of condensate to process Recovery of salts in centrifuge

Plant capacity 150 KLD

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Plant capacity 150 KLDIn operation since year 2012

COCA COLA GOBLEJ - CLOSED WATER LOOP CONCEPT INDIACOCA COLA GOBLEJ - CLOSED WATER LOOP CONCEPT, INDIAWATER BALANCE

Number refers to relative flow %

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Number refers to relative flow %

RO MVRFrom process

100 80100 2

Concentrate

Bio MBR100

FC

18Sludge

FC crystallizator

Clean water to process1

99 Concentrate

CentrifugeSalt

99 Concentrate

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COCA COLA BOTTLE WASHINGCOCA COLA BOTTLE WASHINGANALYSIS

Parameter Unit Evaporator feed (MVR)

Condensate Concentrate

pH 6,5 - 7 7 – 7,5 7 - 7 5p , 7 7,5 7 7,5

Temperature oC 35 - 45 50 - 55 50 - 55

TDS mg/l 10.000 – 12.000 < 150 100.000 -120.000

BOD mg/l

COD mg/lmg/l

Total Hardness

mg/l 200

Evaporator (MVR) recovery 90%

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FLUE GAS CONDENSATE CLEANING - BIO-POWER PLANT, FINLAND

Heat recovered 40 MWFl d t fl 10 l/ (36 3/h)Flue gas condensate flow 10 l/s (36 m3/h)Temperature 50 oCComposition (only salts) NaCl 300 mg/l Na2SO3 500 mg/l Na2SO4 1.200 mg/lTotal salts 2.000 mg/l

TYPICAL COMPOSITION OF FLUE GAS TYPICAL COMPOSITION OF FLUE GAS CONDENSATE

Solids 50 – 1.000 mg/l NaCl 50 – 2 000 mg/l NaCl 50 – 2.000 mg/l Na2SO3 100 – 5.000 mg/l Na2SO4 100 – 5.000 mg/l2 4

Heavy metals 0,1 – 30 mg/l NH3 1 – 250 mg/l Dioxin & Furan 0 – 1 mg/l PAH 0 – 0,01 mg/l Ca 1 – 50 mg/l ( 5 000 mg/l *) Ca 1 – 50 mg/l (…. 5.000 mg/l )

* if Ca is used for neutralisation

COMPARISON OF THREE ALTERNATIVE PROCESS SOLUTIONS COMPARISON OF THREE ALTERNATIVE PROCESS SOLUTIONS FOR FLUE GAS CONDENSATE CLEANING

1. RO alone2. RO + Multi Effect (ME) evaporation3. Multi Effect (ME) evaporation alone

PURIFICATION OF FLUE GAS CONDENSATE WITH ROPURIFICATION OF FLUE GAS CONDENSATE WITH RO

M

Reject to ash humidifyingRejectReject

FEED

Reject to ash humidifying0.3 l/s

Reject0.2 l/s

Reject0.1 l/s

Reject1,5 l/s

25°CM

FEED10 l/s, 50 °C2000 ppm M M

1 l/s

BOILER MAKE UP8,2 l/s

Cooling Pre-filter UF Tank

M

RO EDI

WATER RECOVERY 82% REJECT1,8 l/s (tot.) (= 6.500 l/h)

Conclusion: Reject flow too big, further concentration needed!

PURIFICATION OF FLUE GAS CONDENSATE WITH RO & EVAPORATOR

2-stage evaporator DISTRICT HEATING WATER

Waste heat from boiler1.1 kg/s

Reject to ash humidifying

Reject to ash humidifying0.3 l/s 1. cond.

to boiler1.1 l/s

Reject to ash humidifying0.1 l/sDS = 20%

25°C

FEED10 l/s, 50 °C2000 ppm

Reject0.2 l/s

Reject2 l/s

1 l/s

BOILER MAKE UP

1,9 l/sReject0.1 l/s

25 C

Pre

BOILER MAKE UP9.6 l/s

7.7 l/s

Cooling

WATER RECOVERY 96%

Pre-filter UF

REJECT0.4 l/s (tot.) (= 1.440 l/h)

RO EDI

Conclusion: Reject flow OK, but process could be simpler

PURIFICATION OF FLUE GAS CONDENSATE WITH EVAPORATOR

M

Reject to ash humidifying0.1 l/s

Reject0.1 l/s

FEED10 l/s, 50 °C

3-stage evaporator DISTRICT HEATING WATER

M2000 ppm

M

Reject to ash humidifying0.1 l/sD.S. = 20%

Pre-filter Tank BOILER MAKE UP

9.8 l/s

1. cond.to boiler3 5 l/s

Waste heat from boiler3 5 kg/s

WATER RECOVERY 98%REJECT0.2 l/s (tot.) (= 720 l/h)

3.5 l/s3.5 kg/s

Conclusion: Simplest and most cost effective

VOLUME REDUCTION IN EVAPORATIONVOLUME REDUCTION IN EVAPORATIONFEED CONCENTRATION 5.000 MG/L TDS

Feed at 0,5% TDSCondensate

Polymeric film evaporator

(clean water)

p

Concentrator

Concentrate (dirty water)

Concentrator

Centrifuge/dryer

COST SAVINGS IN WATER RECYCLING BY COST SAVINGS IN WATER RECYCLING BY EVAPORATION

Fresh water cost savings, including possible cleaning costs

Reduced cost for conventional effluent treatment

N f l d h dli No cost for sludge handling

Cost savings in land allocated for conventional treatment

Value of recovered solids (positive or negative)

Heating of the water to the process temperature

With new technology: The savings can be bigger than the operation costs!

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With new technology: The savings can be bigger than the operation costs!

POLYMERIC FILM EVAPORATION COST COMPARISON TO POLYMERIC FILM EVAPORATION COST COMPARISON TO CONVENTIONAL EVAPORATION (”LARGE EVAPORATORS”)

Energy consumption (el = 6 Rs/kWh, steam 1 Rs/kg) Rs/m3 clean water

New technology MVR (12 kWh/m3 + 10 kg steam/m3) 82 Conventional MVR (25 kWh/m3 + 20 kg steam/m3) 170 Conventional ME 1 stage (2 kWh/m3 +1100 kg steam/m3) 1112 Conventional ME 1 stage (2 kWh/m3 +1100 kg steam/m3) 1112 Conventional ME 4 stage (3 kWh/m3 + 280 kg steam/m3) 298

Relative investment cost Relative Low corrosion (incl. sea water) 0,7 – 0,9

M di i 0 6 0 8 Medium corrosion 0,6 – 0,8 High corrosion (high chloride, acids) 0,4 – 0,5

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CONCLUSIONSCONCLUSIONS

Evaporation in general: Almost only tool for zero discharge systems Evaporation is the most powerful tool for removal of dissolved pollutants (salts, organic matter etc.)

But costs are high in conventional evaporators MVR reduces operation costs Scaling and fouling may be a problem

New Polymeric Film technology: Investment and operation costs are considerably Investment and operation costs are considerably

reduced Scaling and fouling problems are more easily managed

R li f i i l dil ffl i Recycling of surprisingly dilute effluent streams is becoming feasible

Waste heat or solar can be efficiently utilized (ME) y

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ADDITIONAL INFORMATIONADDITIONAL INFORMATION

Leif Ramm-Schmidt, Ramm-Schmidt Consulting Ltdleif.ramm-schmidt@rsconsulting.fig

Chandan Kumar, Arvind Envisol Pvt. Limited Limited chandan.kumar@arvind.in

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