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 [email protected]
Chandan Kumar, Arvind Envisol Pvt. Limited Limited [email protected]
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