chemical management effects and side effects on etp and analysis plan (sap) page 015 purpose sap...

CHEMICAL MANAGEMENT EFFECTS

and SIDE EFFECTS ON ETP

AHMET BABA

Sustainable Textile Solutions,

BluWin Ltd.

Textile and Footwear Production IndustryScenario till 2015

1. No unified set of expectations for suppliers that

discharge industrial wastewater.

2. A large quantity of water and if not treated properly,

presents a threat to people and the environment.

3. Further, a lack of consistency between brands around

expectations can lead to confusion within the value

chain.

page

02

Need

Wastewater guidelines

published by different

brands, as well as amongst

multibrand consortia, vary

greatly.

Example: COD

WastewaterGuideline

WastewaterGuideline

page

04

In Nov 2016, ZDHC addresses this issue

with the release of the ZDHC Wastewater

Guidelines

A harmonised set of wastewater

parameters, limit values and test

methods, which will ensure brands and

suppliers are working to the same set of

expectations.

Define a single, unified expectation

concerning wastewater discharge quality that goes beyond regulatory compliance, not only

for conventional wastewater parameters, but also

for hazardous chemicals.

Purpose

WastewaterGuideline

Wastewater GuidelineConventional Parameters

page

06

Parameters

Temperature [°C]

TSS

COD

Total-N

pH

Colour [m-1] (436nm; 525; 620nm)

BODs

Ammonium-N

Total-P

AOX

Oil and Grease

Phenol

Coliform [bacteria/100 ml]

Persistent Foam

Anions

Sulfide

Sulfite

Metals

Antimony

Chromium, total

Cobalt

Copper

Nickel

Silver

Zinc

Arsenic

Cadmium

Chromium (VI)

Lead

Mercury

Wastewater GuidelineConventional Parameters

page

07

The limits determined by evaluating over 1000 wastewater test reports from the

textile and footwear industry.

1. Foundational limit values were met by 90%

2. Progressive limits by 50%

3. Aspirational limits by 20%

Improve the treatment efficiencies by

► Training of personnel,

► Data collection and analysis, and

► Possibly minor capital improvements,

Supplier should begin their journey toward aspirational goals by focusing on

Capacity of those they hire to operate

Maintain their wastewater treatment systems

To collect the appropriate data

Aspirational

Demonstrates best-in-class

performance and strives for

continuous improvement in both

chemicals and wastewater

treatment process knowledge;

creates industry best practices.

Progressive

Demonstrates increasing

knowledge of chemical

management and applies

advanced wastewater treatment

processes.

Foundational

At a minimum, meets legal

discharge requirements and

ensures effective control of ZDHC

MRSL chemicals

Conventional ParametersThree Level Approach

page

08

01 02 03

Wastewater GuidelineMRSL Parameters

1. Alkylphenol (AP) and Alkylphenol Ethoxylates (APEOs) (All Isomers)

2. Chlorobenzenes and Chlorotoluenes

3. Chlorophenols

4. Dyes - Azo (Forming Restricted Amines)

5. Dyes - Carcinogenic or Equivalent Concern

6. Dyes - Disperse (Sensitising)

7. Flame Retardants

8. Glycols

9. Halogenated Solvents

10. Organotin Compounds

11. Perfluorinated and Polyfluorinated Chemicals (PFCs)

12. Ortho-Phthalates - Including all ortho esters of phthalic acid

13. Polycyclic Aromatic Hydrocarbons (PAHs)

14. Volatile Organic Compounds (VOC)

Wastewater Sampling Direct Discharge & Indirect Discharge

page

010

A point source that discharges

wastewater to streams, lakes, or

oceans.

Municipal and industrial facilities that

introduce pollution through a defined

conveyance or system such as outlet

pipes are direct dischargers.

Direct Discharge

The discharge of wastewater to a

treatment facility not owned and

operated by the facility discharging

the pollutants, for example a municipal

wastewater treatment plant or

industrial treatment park.

Indirect Discharge

Sampling Points Facility with own WWTP & direct discharge

page

011

Sampling Points Facility with indirect discharge

Sampling Points Zero Liquid Discharge (ZLD)

Test:-

1. Raw (untreated) wastewater#

2. Any sludge or solids from the ZLD process @

3. Collect a sample of incoming fresh (makeup) water, test# only if

there are any detected MRSL chemicals in the raw wastewater

or sludge/solids

There is no need to test the clean water (RO Permeate)

returning from the ZLD to the manufacturing process.

# ZDHC MRSL v1.1 chemistries. (Tables 2A-2N + As, Cd, Cr(VI), Pb, Hg).

@ ZDHC MRSL v1.1 chemistries. (Table 3).

ZLD• No liquid wastewater is

discharged from the system.

• The only water leaving is that as

vapour and trapped in

sludge/crystallised brine.

WastewaterSampling Point Locations

page

014

Wastewater sampling shall occur at a

point closest to the location where the

wastewater leaves the property of the

facility..

Discharged Wastewater

To assist with point source

identification of hazardous chemicals

in the event the wastewater test result

indicate a hazardous chemical above

the reporting limits.

Incoming Water

Raw wastewater testing will give

further insights into the usage of ZDHC

MRSL chemicals which may be

diverted into the sludge during

wastewater treatment.

Raw WastewaterSludge analysis from wastewater

treatment is considered another factor

in the verification of MRSL compliance

Sludge

WastewaterSampling and Analysis Plan (SAP)

page

015

Purpose

SAP provides a detailed framework for laboratories to

conduct wastewater sampling and analytical services.

Topics Covered

1. Sampling

Types of Samples and Sampling Points/Locations

Sample Collection

Sample Containers and Preservatives

Sample Custody

Sample Shipments

2. Laboratory Analysis/Testing

Sample Receipt, Handling, and Custody

Sample Holding Time

ZDHC Wastewater Parameters

Standard Test Methods

Required Reporting Limits

Quality Systems

Sample Storage

Reporting and Deliverable Requirements

3. Data Validation

WastewaterGeneral Treatment Technologies

page

016

01Pretreatment

Basic screening to remove rags, gravel and sand,

which will block the downstream system

Flow equalisation to balance the flow in batch

operation

Segregation of flow for high pH or stream containing

PVA etc.

03Secondary Treatment

Biological treatment process which use bacteria for

the decomposition of biological degradable organics in

the presence or absence of oxygen

02Primary Treatment

Primary sedimentation with or without chemical

coagulation to settle suspended particle

04Tertiary Treatment

Filtration, disinfection, removal of microbes or

salt using membrane

05Advanced Treatment

Treatment include colour removal, thermal or

membrane based evaporation and salt recovery

Wastewater GuidelineTypical Issues With ETP

Designed to meet the local requirements only

01Need to keep cost down to be competitive

02Limited space restricted some design or additional installations

03Internal communication about ETP load

04

Common Challenges Design Vs Discharge

page

018

Retention time The capacities of the tank and discharge volume of the

effluent should match for a better functioning of the

plant – values are normally 8-16 hours for equalization

tanks.

Capacity of the Tank Ex. equalization tanks capacities should match the

maximum production capacity of the plant,

An oversized tank is good for the process, but a

undersized tank is not desirable, due to low time for

sedimentation


page

019

Bypasses The treatment processes should follow all the

processes, without the options for any bypassing,

overflowing or undertreatment process.

Process control parameters The design of the plant should be able to maintain and

deliver the required parameters as per the local and

international laws.


page

020

Design as per discharge parameters. The plant should able to deliver the discharge

parameters, complying local effluent discharge norms

as well as the international discharge norms. i.e.

ZDHC, etc.

The limitation of designing the WWTP to the local

norms , will have to undergo frequent reinvestments,

with the upgradation or change of local norms.

For example-the plant with the higher discharge COD

values designed as per local norms, need to undergo

revised tanks sizing and process modifications, if the

discharge norms are reduced to match the international

norm.


page

021

Compatibility and treatability The plant should able to deliver the discharge

parameters, which should be able to treat the

processing plant, effluent type and discharge

characteristic of effluent.

The designing should not limit the operation conditions

and treatability.

o Ex. A dye house may plan to invest in printing unit,

which may discharge, solvents and others.

o In such cases, the design limitations should not

deter the investment option to cater the change in

the need of market.

o WWTP should able to accommodate any change

in the process activity , considering the switch

overs and modifications.


page

022

Other parameters affecting the operations.Dissolved oxygen

Impact of the dissolved oxygen levels in incoming

effluent

o Wastewater effluent treatment plants often

contains organic materials that are decomposed

by microorganisms, which use oxygen in the

process.

o The amount of oxygen consumed by these

organisms in breaking down the waste is known as

the biochemical oxygen demand or BOD.

Impact of the dissolved oxygen levels in Discharged

treated effluent

o If more oxygen is consumed than is produced,

dissolved oxygen levels decline and finally affect

aquatic life.


page

023

Other parameters affecting the operations.pH of the effluent and discharge water

As a chemical component of the wastewater, pH has

direct influence on wastewater treatability — regardless

of whether treatment is physical/chemical or biological.

After the identification of parameters — the pollutants or

impurities — that are actually in the wastewater, the

determination of the starting and the ending pH values,

along with a specific treatment procedure should be

determined

The selection of the appropriate chemicals best suited

for treatment, should be determined as per the pH

conditions of the effluent.


page

024

Other parameters affecting the operations.Temperature

The higher temperatures have adverse effects on

settling condition in treatment plant

It has adverse conditions in biological treatment plants.

Conventional parameter Temperature – Impact

1. High temperature affect chemical reaction

rates and aquatic life.

2. Higher temperatures have adverse effects on

settling condition in WWTP.

3. Also, has adverse conditions in biological

treatment plants

.

Conventional parameter Temperature – Control

• Cooling Towers

• Surface Aeration

• Flow Mixing

Conventional parameter Colour – Impact

• Fresh wastewater - light brownish grey

• Old wastewater - dark grey and black.

• The dark grey and black color is due to

formation of sulfide produced under

anaerobic conditions reacts with the

metals present in wastewater.

• Several color-causing substances are

micro- toxic to aquatic life.

• The discharge of strongly colored

wastewater from dyeing operations could

be o adverse aesthetic effects,

o carcinogenic,

o mutagenic and

o detrimental to our environment.

• Coagulation (Color Removing Agent )

• Advance Oxidation Process

• Fenton Regent

• Activated Carbon Filter

• Membrane Technology

• Decoloration

Conventional parameter Colour – Control

Conventional parameter pH – Impact

• pH of water move away from range (6.5-8.5)

can stress animal systems and reduce

hatching and survival rates. A

• Acidic conditions (low pH) or basic conditions

(high pH) alter the structure of the enzyme

and stop growth.

• Most microorganisms do well within a pH

range of 6.5 to 8.5.

• Abnormal or irregular pH in biological

treatment processes can result in a significant

decrease efficiency of secondary treatment.

Conventional parameter pH – Control

• pH Neutralization (Equalization )

• Coagulation (FeSO4)

• Acid (H2SO4)

• Alkali (NaOH)

• Auto dosing of Acid/Alkali

• In Line pH Check

• Primary

• Secondary

• Tertiary

Conventional parameter pH – function in heavy metal removal

Solubility of Metal hydroxides as a

function of pH

Conventional parameter Biological Oxygen Demand (BOD)

page

032

• BOD is a characteristic of water (not a pollutant)

• When biodegradable organic matter is released

into a water body, microorganisms feed on the

wastes, breaking them into simpler organic and

inorganic substances.

• When this decomposition occurs in aerobic

environment the process produces non-

objectionable, stable end products like CO2,

SO4, PO4 and NO3.

• High BOD means microorganisms would likely

deplete the dissolved oxygen breaking down the

waste

Wastewater GuidelineDissolved Oxygen (DO)

Impact of the DO levels in incoming effluent

• Wastewater effluent treatment plants often

contains organic materials that are decomposed by

microorganisms, which use oxygen in the process.

• The amount of oxygen consumed by these

organisms in breaking down the waste is known as

the biochemical oxygen demand or BOD.

Impact of the DO levels in Discharged treated

effluent

• If more oxygen is consumed than is produced, DO

levels decline affecting the aquatic life.

•Activated Sludge process

•Anaerobic treatment (MBR)

•Sand Filters

•Membrane (UF, MF, RO)

Conventional parameter Biological Oxygen Demand (BOD) – Control

Conventional parameter Chemical Oxygen Demand (COD)

• COD is a measured quantity that does not

depend on microorganisms.

• To calculate the concentration of oxygen for non

biodegradable materials a strong oxidizing agent

known as potassium dichromate will be used

• The COD test is much quicker than BOD test,

but it does not distinguish between the

biodegradable and non biodegradable organic

matter.

• Roughly the BOD/COD is 0.4 to 0.8

• Coagulation & Flocculating

• Advanced Oxidation Process

• Process Filtration and Adsorption with Activated Carbon ( ACF)

• COD Reducing process by Fenton Reaction

• Reduce COD with Oxidator

• Membrane (UF, MF & RO)

Conventional parameter Chemical Oxygen Demand (COD) –Control

Conventional parameter Heavy Metal – Impact

Most common: Arsenic, Lead, Mercury, Cadmium

Less common: Chromium, Copper, Nickel, Zinc

• Toxic metals can cause contamination of water and

land and also affect aquatic life

• In larger amounts cause acute and chronic toxicity.

• Linked to learning disabilities, cancers and even

death

• Heavy metals have inhibitory effects on the

biological treatment process at the WWTP

Conventional parameter Heavy Metal – Sources

Copper Copper salts are used to fix direct dyes and to enhance the light fastness on nylon

Phthalocyanine Colours

Nickel Phthalocyanine Colours

Screen mesh used for printing

Cobalt

Cobalt and chromium are applied particularly in dyes for wool: almost every wool mordant dye uses chromium

compounds

Cobalt, chromium and occasionally copper and nickel form part of the most commonly used dyes, especially dyes

for leather materials, nylon and wool.

Phthalocyanine Colours, Acid dyes, Impurities in Chromium & Manganese

Chromium 6+

Chromium salts to improve wash fastness on direct dyed material

Also on acid dyed silk and wool

Potassium Dichromate is used for oxidation of vat and sulphur dyes

Substances such as potassium chromate and potassium dichromate, both of which contain Cr (VI) may be added

as part of the dye manufacturing processes.

The chromium containing C.I. Mordant Black 11 is one of the most widely used dyes in the world.

Chromium

Total

Tannin of leather

Chromium-based dyes is essential for the fast black dyeing on wool and nylon

Mercury

Contaminant from caustic soda plants manufactured by mercury cells routes

In ETP chemicals impurity

Vat, Sulfur anthraquinone based byes (Sulphonation of naphthalene)

Zinc

Cationic dyes contain zinc as well as trace concentrations of mercury, cadmium and

arsenic as impurities.

zinc sulfoxylate formaldehyde Reducing agent for discharge printing

Fluorescent pigment

GI pipeline

Arsenic Cationic dyes contain zinc as well as trace concentrations of mercury, cadmium and


Lead In ETP chemicals impurity

Cadmium Cationic dyes contain zinc as well as trace concentrations of mercury, cadmium and


Antimony Antimony improves wash fastness properties on nylon fibers.

Drying agent on prints (For quick curing)

Barium Textile Dyeing

Barium activity number for degree of mercerization

Tin Fluorescent pigment

Conventional parameter Heavy Metal – Sources

Conventional parameter Heavy Metal – tips for improvement of Zn2+, Ni2+, Cd2+, and Pb2+

Coagulation & Flocculation Ion Exchange RO System

• Foam is an important quality of the treated

wastewater.

• A visual inspection of the final effluent should be

carried out to determine whether any foam

generated quickly dissipates and thus does not

build up in channels or the receiving waters.

• There should be no floating solids on treated

wastewater effluent.

• Aerobic treatment - Quality of foam generated

can tell you the process status

Conventional parameter Foam

• Foam type 1: white, frothy, not particularly stable foam

• Foam type 2: white/brown foam, stable and containing fine particles of mixed liquor solids

• Foam type 3: dark, stable, heavy, ‘chocolate mousse’, foam

Conventional parameter Foam

• Coliform bacteria are a commonly used bacterial indicator of water pollution, although not an actual cause of disease.

• Other microorganisms sometimes found in surface waters which have caused human health problems such as Salmonella, Norovirus or Parasitic worms

• Many microorganisms, especially coliform group, can cause various types of waterborne diseases.

Conventional parameter Coliform – Impact

Ozonation UV

disinfection Chlorine Di Oxide

Chlorine Hypochlorite

Conventional parameter Coliform – Control

Wastewater GuidelineSome common root causes for failures

PARAMETERS/SUBSTANCE SOURCES/REASONS FOR DETECTİONS

Temperature Inefficient cooling towers for wastewater

pH fluctuating effluent load, Inefficient pH monitoring

Total Suspended Solids Inefficient sand filtration etc.

Biological Oxygen Demand Inefficient secondary treatment such as activated sludge process

Chemical Oxygen Demand Inefficient primary treatment such as coagulation and flocculation

Antimony1. Antimony trioxide is use as catalyst in polyester fibers2. Drying agent on prints (For quick curing)

Arsenic1. Cationic dyes contain zinc as well as trace concentrations of mercury, cadmium and arsenic as impurities.

Cadmium 2. Cationic dyes contain zinc as well as trace concentrations of mercury, cadmium and arsenic as impurities.

SUBSTANCE SOURCES/REASONS FOR DETECTİONS

Chromium

1. Chromium salts to improve wash fastness on direct dyed material, also on acid dyed silk and wool2. Potassium Dichromate is used for oxidation of vat and Sulphur dyes 3. Substances such as potassium chromate and potassium dichromate, both of which contain Cr (VI) may be added as part of the dye manufacturing processes.4. The chromium containing C.I. Mordant Black 11 is one of the most widely used dyes in the world.

Cobalt

1. Cobalt and chromium are applied particularly in dyes for wool: almost every wool mordant dye uses chromium compounds 2. Cobalt, chromium and occasionally copper and nickel form part of the most commonly used dyes, especially dyes for leather materials, nylon and wool. 3. Phthalocyanine Colours, Acid dyes, Impurities in Chromium & Manganese

Copper1.Copper salts are used to fix direct dyes and to enhance the light fastness on nylon 2. Phthalocyanine Colours

Lead 1. In ETP chemicals impurity


PARAMETERS/SUBSTANCE

SOURCES/REASONS FOR DETECTİONS

Mercury1. Contaminant from caustic soda plants manufactured by mercury cells routes 2. In ETP chemicals impurity3. Vat, Sulfur anthraquinone based byes (Sulphonation of naphthalene)

Nickel 1. Phthalocyanine Colours

Zinc

1. Cationic dyes contain zinc as well as trace concentrations of mercury, cadmium and arsenic as impurities.2. Zinc sulfoxylate formaldehyde Reducing agent for discharge printing3. Fluorescent pigment

Colour Inefficient dyeing processes or printing paste washing

Coliform Mixing of domestic and industrial waste for treatment, Contaminated ETP

Foam Use of excessive detergents in processes


askyourself

? Is the design capacity clear to the ETP responsible

person?

? What are the design parameters in each step?

? Does the factory monitor key parameters? Are such

records available?

? Is monitoring conducted manually or automatically?

page

048

To identify if a ETP is functioning or just running, questions to ask:

thank you.

AHMET BABA

0 533 593 1331

chemical management effects and side effects on etp and analysis plan (sap) page 015 purpose sap...

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