New Membrane Innovations to Reduce Total Cost of Operation (TCO) of ZLD Systems in Distillery Plants

Ravindra Yeleswarapu

Nitto in Numbers: Transforming Ourselves Constantly

1918Year founded

$7.2Billion in sales

109Companiesworldwide

29,600Employeesworldwide

13,500Products

70Markets

15,000Patent families

granted or in progress

Nitto Named One of 2018-19 Derwent Top 100 Global Innovators, Marking its Eighth

Consecutive Year on the List

Oceanside, CA, USAFounded: 1963

Shanghai, ChinaFounded: 2001

Shiga, JapanFounded: 1986

Manufacturing FacilitySales and/or Technical Service Office

Hydranautics,R&D andProduction RO/NF/UF/MF Nitto China, Songjian,Assembling 4” RO element

Shiga, Japan,HQ of Global Membrane Div. R&D and Production RO/NF/UF/MF

Nitto Global Membrane Division

Industries We Serve

Chemical Dairy Electronics, LCD Food & Beverage Industrial – Waste Water

Maple Municipal – Potable Water Municipal – Waste Water Oil & Gas Petrochemical & Refinery

Pharmaceutical Power Generation Pulp & Paper Semiconductor Textile

Waste Water Treatment Challenges & Our

Solutions

Industry’s Conundrum

• Water Scarcity • Stricter

Regulatory Norms

• Sustainability Greener Future

3Rs• Reduce,

Reuse & Recycle

• High Treatment Cost of Water• Huge Impact on the Profitability

Zero Liquid Discharge (ZLD)

ZLD Challenges• Economic Viability

• Varying water availability and cost of water

• High Capex and Opex• High cost of the treatment systems / equipment ( RO, MVRE, MEE, Crystallizer)

• Cost of thermal evaporators RO :: 100:20

• Scale up of the systems make it more economical Hence, CETPs

• High energy requirement Thermal Evaporation Systems• Opex of 1000 KLD plant for 6 years is equivalent 3 times the capex *

• Non- Uniform Policy • ZLD implementation / PCB norms are a subject of state policy rather than the Central

Policy Significant impact on the cost of production

• Production cost (for textiles increases from 14% 42% (Without ZLD)

• Changing scenario Center driving the new policy implementations

• Solid Waste /Toxic waste handling• Technology

• Currently the treatment scheme includes Pretreatment Secondary (Biological) Treatment Tertiary Treatment (3/ 4 stage RO) Thermal Evaporation (MVRE/ MEE) Crystallization• With current available RO technology ~ 95% of the water is recovered High Energy

Consumption

7

Typical ZLD System Operating CostPre Treatment,

62, 33%

RO, 28, 15%Evaporator, 66, 35%

Manpower + Sludge Disposal,

33, 17%

Rs/KL

Innovation Needs

1. Maximize the RO reject concentration > 120,000 ppm of TDSa. Reduce the energy consumption in the evaporator b. Reduce the overall Opex (Evaporation cost) by ~ 50%

2. Minimize the foulinga. Extend the mean time between cleanings

i. From the current rate of once /week Once/fortnightb. Increases the membrane lifec. Reduces the Life Cycle Cost of the membranesd. Reduced chemical consumption & cost

3. Generate pure salt (Specific to Textile Industry)a. High Purity & Color free Na2SO4 can be reutilized in the process

For a sustainable ZLD system, Opex reduction is the Key

Low Fouling Specialty RO Membranes for ZLD-MLD Systems

• New low fouling technology instead of SWRO

• High salt rejection with thicker feed spacer

PRO-LF1

Test Conditions

Feed MgSO4 Applied pressure Permeate Recovery rate Temperature Feed pH

2,000 ppm 0.76 MPa (110 psi) 15% 25° C (77° F) 6.5 – 7.0

PRO-XS1S P E C I F I C AT I O N

Specified Performance & General Product Description

Nominal MgSO4 rejection 99.8%

Minimum MgSO4 rejection

99.7%

Permeate flow 8,500 gpd (32.2 m3/d)

Active Membrane area 400 ft2 (37.2 m2)

Feed spacer thickness 34 mil (0.864 mm)

Ultra-high Pressure Membranes for Challenging Industrial Process Applications

• Can operate at pressures up to 124 bar (1800 psi)

• Can be used to reduce industrial waste stream by 50%

• Ideal for treating industrial waste steams in textile, pulp & paper, oil & gas industries

PRO-XP1

Distillery Condensate Generation Process

13

Distilation Process

Spent Wash (effluent)

Primary Evaporator

Conc Spent Wash

Multiple Effect Evaporator (MEE) Condensate Molasses Dilution & Cooling Tower

Remaining Concentrate Effluent

Incineration & Bio-composting

This condensate requires treatment for-1) COD reduction from 4000 to

Treatment Flow Diagram

14

CONDENSATE COLLECTION TANKCONDENSATE

FROM DISTILLATION PROCESS

1 OR 2 STAGES

TREATEDWATER TANK

DUAL MEDIAFILTER

ALKALI DOSING

MICRON FILTER

ANTISCALANT DOSING

RECOVERY >75%

REJECT FOR PRESS MUD

REVERSE OSMOSIS

EXISTING

CPU Process Flow Diagram

CONDENSATE COLLECTION TANK

CONDENSATE FROM DISTILLATION PROCESS

1 OR 2 STAGES

TREATED WATER TANK

DUAL MEDIAFILTER

ALKALI DOSING

MICRON FILTER

ANTISCALANT DOSING

RECOVERY >75%

REJECT FOR PRESS MUD

REVERSE OSMOSIS

PROPOSED

MSIL GURGAONPROPOSED STP WATER MANAGEMENT

SEWAGE COLLECTION TANK

SEWAGE COLLECTION TANK

GRIT REMOVAL, O&G REMOVAL AND SCREENING

SLUDGE FOR DISPOSAL

SEWAGE WATER FROM MAIN PLANT1200 KLD

SEWAGE WATER FROM ANCILIARY UNITS300 KLD

AERATION TANK

CLARIFIER

TREATED WATER TANK

MULTI GRADE FILTER

CARBON FILTER

ULTRAFILTERATION

REVERSE OSMOSIS

SLUDGE FOR DISPOSAL

WATER FOR REUSE (TOTAL RECOVERY 95%)

BOD

PRO-LF1Low Fouling Robust RO

Specialty RO Membranes for CPU System

Key Features and Advantages of PRO-LF1

Thicker feed spacer (34 mil with 400 ft2)• Possible to reduce Dp• Possible to reduce fouling

potential• Improve CIP effects

Air release slit on the seal carrier• Quick air release

reduces element burst risk

PRO-LF1Low-Fouling

RO

High salt rejection and low fouling flat sheet membrane• Stable concentration & fouling

resistance at high salinity and high COD

• Reduce CIP frequency and enhance the CIP recovery

Test Conditions

Feed NaCl Applied pressure Permeate Recovery rate Temperature Feed pH

32,000 ppm 5.5 MPa (800 psi) 10% 25° C (77° F) 6.5 – 7.0 17

PRO-LF1S P E C I F I C AT I O N

Specified Performance & General Product Description

Nominal NaCl rejection 99.8%

Minimum NaCl rejection 99.7%

Permeate flow 7,700 gpd (29.1 m3/d)

Active Membrane area 400 ft2 (37.2 m2)

Feed spacer thickness 34 mil (0.864 mm)

Flat Sheet Membrane Improvement

• PRO-LF1 of modified flat sheet membrane shows neutral charge.

18

Positive charge

Negative Charge

Mem

bran

e su

rfac

eZe

ta p

oten

tial

2 4 6 8 10 12-40

-20

0

20

pH

Neutral Charge

(mV)

PRO-LF1

Conventional RO

Flat Sheet Membrane Improvement• PRO-LF1 of modified flat sheet membrane has more hydrophilic surface.

19

0

10

20

30

40

50

Conventional SWRO PRO-LF1

Con

tact

Ang

le (°

)

Conventional RO

Protein Absorption Test• PRO-LF1 shows slight protein absorption force which indicates between

30% to 90% less organic fouling potential

20

0.00

0.10

0.20

0.30

0.40

pH5 pH7

Protein(BSA) Absorption TestAFM(Atomic Force Microscope)

Abso

rptio

n Fo

rce

Strong

Weak

Conventional ROPRO-LF1

Case Study: Tannery ZLD Plant

21

Tannery CETP (3-Stage RO System)

Total no. of trains 3

3 stages per train 2:1:1 (6 elements / vessel) at 65%

Membrane type 1st Stage of Train 3 PRO-LF1

1st Stage of Train 2 Conventional RO

Start-up October 2018 (150 days of operation)

Feed flow 13.0 m3/hr

Permeate flow 5.7 m3/hr (1st Stage) Rec = 44%

Feed quality to RO

pH 6.0 – 6.5

Turbidity < 2 NTU

SDI < 5.0

TDS 15,000 – 16,000 ppm

Hardness 1,100 ppm

COD 600 ppm

Equalization → Clarifier → Aeration → Secondary clarifier → Tertiary Clarifier → DMF 1 and 2 → UF with 12 HYDRAcapMAX 80 → RO → Evaporator

Performance of PRO-LF1 vs Conventional RO• PRO-LF1 permeate flow shows more stable than that of Conventional RO when treating feedwater with 600 ppm COD• PRO-LF1 shows better recoverability after CIP than that of Conventional RO• The CIP frequency reduced 50%

22

CIP Conditions:NaOH / EDTA & HCl45 min. Circulation / 30 min. soaking / 45 min. circulation / 5 hrs. soaking / flushing

0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

0 20 40 60 80 100 120 140 160

m3/

h

days

Permeate Flow - Normalized

Conventional RO PRO LF1

23

New Ultra High Temperature RO Element

Product Permeate Flow ***

(gpd)

Rjection

(%)

Membrane Area (ft2)

Maximum Pressure

(bar)

Maximum Temperature

(C)

PRO-XT1*) 8,000 99.5 335 82.7 (at 25 C)

85 (at 18 bar)

PRO-XT2**) 5,300 99.7 325 41 (at 65 C)

85(at 18 bar)

*Test condition : 1,500 ppm NaCl; 1.55 MPa; 15% recovery; 25C ; 6.6-7.0 pH**Test condition : 32,000 ppm NaCl; 5.5 MPa; 15% recovery; 25C ; 6.6-7.0 pH***Permeate flow value is at initial test

Ultra-high Pressure Membranes for Challenging Industrial Process Applications

• Can operate at pressures up to 124 bar (1800 psi)

• Can be used to reduce industrial waste stream by 50%

• Ideal for treating industrial waste steams in textile, pulp & paper, oil & gas industries

PRO-XP1

Industrial Water Recovery Actions: Typical

Wastewater (1000-3000 TDS)WW Discharge Fee @ $2-22/m3

10% Loss of Water @ $1.8 /m3

Media or Membrane Pretreatment

Oil/Water Separation

Lime or Zeolite Softening

26

10X Concentrated Wastewater

Brine

2 Stage Brackish RO4k - 12k TDS

Brine

1-2 Stage Seawater RO10k – 70k

90% rec

Industrial Water Recovery Actions: ZLD

27

Media or Membrane Pretreatment

Lime or Zeolite Softenin

Oil/Water Separation

2 Stage Brackish RO4k - 12k TDS

1-2 Stage Seawater RO10k – 70k TDS

Brine

Wastewater (1000-3000 TDS)

ZLD

Crystallizer

Evaporator250k TDSSalt Waste

Brine

BrineIssue #2Issue #3

Issue #1

Extreme High Pressure RO Membranes –PRO- XP1

28

Parameter PRO-XP1Standard Test Condition

800 psi (5.5 MPa)32,000 ppm NaCl

Extreme high pressure RO with durable

construction

Nominal NaCl rejection 99.8%

Permeate flow 8,000 gpd(30.3 m3/d)

Active Membrane area 330 ft2 ( 30.7 m2)

Feed spacer thickness 34 mil (0.86 mm)

Maximum Pressure 1800 psi (124 bar)

• Operates as highest feed pressure

• Excellent rejection over long-term operation

• Extra robust construction to handle difficult wastewater applications

• Thicker feed spacer to reduce foulant blockage

Extreme High Pressure RO

PRO-XP1

New Specialty RO/NF Membranes for ZLD System

• PRO-XS series High selective separation of valuable salt solutions• PRO-LF1 New low fouling technology instead of SWRO• PRO-XP1 Higher concentration to downsize post treatment

29BWRO

PRO-LF1

PRO-XP1

Solidification / Thermal Process

A

High salinityTDS 6-8%

Water for reuse

Water for reuse

High salinityTDS 1-4%

Feed water after pretreatment TDS >0.8%

Mixed ions TDS 12%

1st Concentration(2 stages)

2nd Concentration(2-3 stages)

3rd Concentration(single stage)

C

B

A

Na+, Cl-

Na2SO4 Rich Solution

SWRO

PRO-XP1

NaCl Rich solution) (purity grade)

PRO-XS

NF

Mixed IonsCl, SO4, Na

Solidification / Thermal Process

Solidification / Thermal Process

Water for reuse

C

B

Reuse toprocess

30

THANK YOU

Slide Number 1Nitto in Numbers: Transforming Ourselves ConstantlyNitto Global Membrane DivisionIndustries We ServeWaste Water Treatment �Challenges & Our SolutionsIndustry’s Conundrum�ZLD ChallengesTypical ZLD System Operating CostInnovation Needs��Slide Number 10Slide Number 11Slide Number 12Distillery Condensate Generation ProcessTreatment Flow DiagramSlide Number 15Key Features and Advantages of PRO-LF1Slide Number 17Flat Sheet Membrane ImprovementFlat Sheet Membrane ImprovementProtein Absorption TestCase Study: Tannery ZLD PlantPerformance of PRO-LF1 vs Conventional ROSlide Number 23New Ultra High Temperature RO Element Slide Number 25Industrial Water Recovery Actions: TypicalIndustrial Water Recovery Actions: ZLDExtreme High Pressure RO Membranes – PRO- XP1New Specialty RO/NF Membranes for ZLD SystemSlide Number 30