INTRODUCTION

PRESENTATION ON WATER AND RESIN.

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WATER IS PRECIOUS. WE TREAT IT WITH SPECIAL CARE!! 4/59

Water

Water is most important raw material used in industry.

It has good heat carrying capacity. It is a universal solvent. Natural water is seldom pure. Water gets contaminated due to contact with air, soil or industrial effluent.
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Water Sources
Surface : River, Creek, Pond & Lake Deep and shallow wells, spring & mine 7/59

Ground Sea

: :

Major Impurities of Water

Non ionic & undissolved Turbidity, silt, mud, dirt & other suspended matters. Colour, organic matter, colloidal silica, micro-organisms, plankton, bacteria, oil and corrosion products. Gaseous Carbon dioxide, hydrogen sulphide, ammonia, methane, oxygen, chlorine, etc.

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Impurities of Water
Generally water is not suitable for any use without some treatment.
Impurities present are harmful depending upon
Nature, source and amount present End use of the water. Tolerance limits for various industries.

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Major Impurities of Water

Ionic & Dissolved
CATIONIC
Calcium Magnesium Sodium Potassium ammonium Iron
Manganese etc.

ANIONIC
Bircarbonate Carbonate Hydroxide Sulphate Chloride Phosphate Silica & Organic matter

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Impure Water
Harmful effects of impure water : Scale - deposition Corrosion Decolorisation of product Taste, colour, microbiological contamination imparted due to impurities
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Water Analysis
The chemical examination of water is very important for :

Selecting suitable water supply Selecting proper treatment scheme Designing the plant Trouble shooting
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Units for reporting Water Analysis

1. ppm as ions or mg/lit

2.

3.

4.

Equivalent per million (epm) epm = ppm eq.wt. of ion ppm as CaCO3 = ppm as ion x 50 eq.wt. of ion Grains per gallon as CaCO3 = ppm as CaCO3 17.1

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Some terms in water analysis

WATER SAMPLING.

Turbidity : It is finely divided suspended matter, clay silt and/or organic matter. Conductivity :The ability of a solution to carry electric current. Measured as micro mhos/cms.

pH :The scale for expressing acidity oralkalinity

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Some terms in water analysis

(Contd...)

Alkalinity

The total of bicarbonate, carbonate and hydroxide alkalinity Equivalent Mineral Acidity (EMA) Chlorides, sulphates and nitrates associated with cations Hardness :Sum of Calcium and Magnesium. Other divalent or trivalent cations such as Iron, Barium, 15/59

Some terms in water analysis

(Contd...)

Total cation. Total hardness + Sodium + Potassium. Total anion. EMA + Silica + CO2

Residual Chlorine The amount of free chlorine after satisfying chlorine demand (usually 0.1 to 0.5 ppm) Total Dissolved Solids (TDS)

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Some terms in water analysis

(Contd...)

Total Suspended Solids (TSS) The solids which can be filtered off. Silica It is soluble silica or reactive silica The non - reactive silica

Colloidal Silica :

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Some terms in water analysis

(Contd...)

Chemical Oxygen Demand (COD) The amount of oxygen consumed for oxidising organic and oxidisable inorganic matter.

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Water Treatment
The basic water treatment processes are limited. Combination and variation of these are used to treat water for desired end use.

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Treatment for Non - Ionic Impurities

Gravity settling Filteration

Different Media : - Sand, Anthracite - Active Carbon - Polymer Bead - Multimedia Filters - Iron Removal Filters
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Treatment for Non - Ionic Impurities

Water pretreatment. Chemical Coagulation

Inorganic Coagulant :
- Alum, Iron Salts, etc.

Organic flocculant : - Cationic, Anionic, Nonionic, Polyelectrolyte

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Treatment for Dissolved Ionic Impurities

Chemical Precipitation
Hardness

and alkalinity removal by lime soda process (hot or cold) Iron removal

Ion Exchange Technique Membrane Technique

Electrodialysis

Osmosis Evaporation

Reverse

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Ion Exchange
Ion exchange is a reversible process. The ions exchanged with stoichiometrically equivalent amounts of ions of the same sign.
After the ion exchange, the exchanger material can be brought back to original form by suitable reaction, called regeneration.
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Advantages of Ion - Exchange Technique

Ambient temperature operation Instantaneous treated water Take care of fluctuation of load Easy waste disposal Cheaper to operate

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Application of Ion Exchange in Water Treatment

Water softening Partial demineralization Demineralization (with or without silica removal) Mixed bed polisher Condensate Polishing. Heavy metal recovery. Special application

Alkalinity

reduction Sulfate removal Nitrate removal Fluoride removal

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Major applications of Ion Exchange Resins

Water treatment Purification and decolourisation of sugar Purification and recovery of drugs, vitamins, amino acids, etc. Purification of DMF, Glyoxal, Caprolactum. Recovery of metals like Thorium, Uranium, Gold Silver, etc.
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Major applications of Ion Exchange Resins (Contd...)

Catalyst in esterification, condensation, etc. In medicines for tablet disintegration, toxic removal as antacids. In water analysis Purification of brine. Removing hazardous constituants from industrial effluents.
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Ion Exchangers
Insoluble solid material carrying exchangeable cations or anions

Ion Exchange Resins

Cation Exchange

Anion Exchange

WAC

SAC

WBA

SBA

Type I

Type II

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Properties of Ion Exchange Resins

Particle

Size : Purely hydraulic and kinetic influence on the ion exchange process. 0.3 - 1.2 mm size is satisfactory for industrial applications. Content : It is bound water related to cross linking. About 45 - 55 depending on type of resin. Gives valuable information on resin under use
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Moisture

Properties of Ion Exchange Resins

(Contd...)

Density : Ion exchange resins are sold on volume basis, hence density measurement is necessary. Density difference of cation and anion exchange resins is used for MB operations.

Porosity :
Related to degree of cross linking, influences capacity & selectivity. Functional groups are present throughout the resin body. Pores provides path for exchanging & exchanged ions. Pores can be micro or macro in size.
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Properties of Ion Exchange Resins

(Contd...)
Cross

linking : Influences capacity, moisture and swelling

Higher cross linking : Less moisture and swelling. Hard and brittle. More hemispherical and oxidation resistance. Less exchange rate
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Properties of Ion Exchange Resins

(Contd...)

Lower Cross Linking : More moisture and swelling. Soft and mechanically weak. Less chemical and oxidation resistance. More exchange rate

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Properties of Ion Exchange Resins

(Contd...)

Swelling : It is volume change due to change in surrounding medium. Depends upon medium, resin matrix. Ionic group present and type of counter ions
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Properties of Ion Exchange Resins

(Contd...)
Total

Exchange Capacity : It is the capacity obtained from the total quantity of counter ions that is capable of exchange per unit weight or volume of either dry or swollen resin Capacity : The capacity that could be realised in a column under a set of selected conditions.
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Operating

Properties of Ion Exchange Resins

(Contd...)
Kinetics

(speed of exchange reaction) :

It is influenced by cross linking, functional groups, particle size, solvent and temperature.
Stability

During service and regeneration, resin is subjected to expansion and contraction. Oxidising agents attack the resin. There is mechanical attrition. All these influence resin life and economics of operation 35/59

Selectivity

At low concentration in aquous medium and at ordinary temperture

The exchange potential increased with increasing valence. Na+ < Ca++ < Al+++ < Th++++ If valence is constant, exchange potential increases with increase in atomic number. Li < Na < K < Rb < Cs Mg < Ca < Sr < Ba F < Cl < Br < I 36/59

Selectivity (Contd...)

At higher concentration the difference in exchange potentials of ions of difference valence diminish and in some cases the lower valence has the higher exchange potential (Na+ Vs Ca++)

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Selectivity (Contd...)
Softening

Ca ) HCO3 R - Na Na (Cl + R Mg) SO4

Regeneration

(HCO3 ( (SO4 Ca) Na - R + ) Cl Mg)

(Ca) Cl + (Mg

Ca ) ) R + NaCl Mg)

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Partial Demineralization
By Split Stream (Softener + Dealkalizer) (When alkalinity is high and hardness is permanent.) Strong Acid Cation Exchanger in H+ form :
Ca Mg Na ) HCO3 ) Cl + H - R ) SO4 Ca) Na) (HCO3 Mg) R+H (Cl (SO4

Strong Acid Cation Exchanger in Na+ form :

Ca Mg Na ) HCO3 ) Cl + Na - R ) SO4 Ca) Mg) R+Na Na) (HCO3 (Cl (SO4

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Partial Demineralization (Contd...)

By WAC (when Alk. high & TH < Alk)
Ca Mg Na ) ) HCO3 + R - H ) H2CO3 R ( Ca ( Mg + H2CO3 ( Na H2O + CO2

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Ion Exchange Resin - Properties

SAC :

pH range 0 - 14 Excellent physical & chemical stability Swelling Na+ H+ 7% H+ form used in DM process and MB Reg. by 4-8% HCl or 1.5 - 5% H2SO4 (*) Max op. temperature 120 C (250 8F) (*) Regeneration is stepwise NA+ form used in softening process Reg by 5 - 15% NaCl solution Max op. temperature 140 C (2808F)

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Ion Exchange Resin - Properties

(Contd...)
WAC

High exchange capacity Excellent physical & chemical stability pH range 5 - 14 Reg. by 2 - 4% HCl or 0.7 to 4% H2SO4 (*) (*) Regeneration is stepwise High regeneration efficiency Regeneration by 120% of stoichiometric qty
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Ion Exchange Resin - Properties

(Contd...)
WAC

(Contd..)

Can be regenerated thoroughfare Higher selectivity for divalent cations. Hence cannot be regenerated directly by salt Takes cations associated with alkalinity. Hence used for dealkalizing. Max. op. temp. 100 C (212 F) Swelling H+ Na+ 100%
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Ion Exchange Resin - Properties

(Contd...)
WBA

No salt splitting capacity in OH- form. Can take anions only associated with strong acids. High reg. efficiency. Reg. by 120% of stoichiometric qty. Reg. by 1-5% NaOH Can be regenerated thoroughfare High operating capacity. pH range 0 - 9 Max. op. temperature 80 C Swelling OHCl- 20% 44/59

Ion Exchange Resin - Properties

(Contd...)
SBA

- Type I and Type II :

Used for DM process and MB Can split salts. Reg. con. 4 - 8% NaOH Swelling ClOH- 9% Max op. temp 60 C (140 F) for type II 80 C (175 F) for type I Both the types can removal all anions
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Ion Exchange Resin - Properties

(Contd...)
SBA

- Type I and Type II :

Type II has high operating capacity More susceptible to oxidation Loosing of SBC is bit faster Regenerate some what more easily Type I has better thermal and oxidative stability, maintain SBC for a longer period Type I has better resistance to organic fouling than Type II
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Demineralization
Strong

Acid Cation Exchanger : Ca ) HCO3 Ca) (HCO3 Mg) Cl + R - H Mg) R+H (Cl Na ) SO4 Na) (SO4 Anion Exchanger : (HCO3 (HCO3 H (Cl + R - OH R - (Cl +H2O (SO4 (SO4
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Regeneration Process
The

process to bring back the exhausted resin to original or usable form is regeneration. The reaction is opposite to service reaction. There are two methods for regeneration cocurrent and counter current method.

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Back Washing
Back washing is done for : Loosening the bed Re-classifying the bed To remove dirt and filtered matter To separate resin in MB
By back washing, more uniform distribution of fluid is obtained in subsequent down-flow operation.

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Back Washing
Pressing water (*) in upward direction to expand the bed to about 50%.
(*) Raw water for SAC. Decationised (and degassed) water for SBA. SBA outlet for MB
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Regeneration (Injection)
According to the resin by HCl, H2SO4 or NaOH, the major factors affecting the degree of regeneration are :
Composition of the exhausted bed Flow rate Contact time Temperature Purity of regenerant Conc. of regenerant Amount of regenerant applied (Reg. level)

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Slow Rinse
It is extended regeneration. Hence at regeneration flow rate generally by 2 BV of water

Fast Rinse :
To remove traces of regenerant. service flow rate. Done at

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Counter Current Regeneration

To

minimise leakage and get better quality effluent No frequent back wash given. Provision is made to avoid fluidizing of the bed and then regenerant is passed in opposite direction of service Back wash is given only when necessary but followed by double regeneration
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Fouling of Ion Exchange Resins

It is covering of exchange sites and / or obstructing ion exchange process.

Major Foulants :

Turbidity and mud Oil & grease. Iron & Calcium. Microbiological &Organic fouling. Silica fouling. Oxidation due to Cl2. Thermal degradation -- Variation in temperature.
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Prevention is better than cure !!!

Many a times fouled resin cannot be completely cured. Fouling of resin can be treated by different methods according to the nature of foulants.

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Trouble Shooting
Major causes in general for less OBR :

Insufficient regeneration Increased load Over running in previous run Fouling Resin loss (quantity & quality) Malfunctioning of up-stream unit/s Excessive rinsing
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Trouble Shooting
Major causes in general for poor quality :

Mechanical problem Chemical precipitation, silica precipitation. Improper separation and improper mixing (MB) Wrong or misleading analysis hence apparent poor quality
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Resin Sampling
Sample should be taken from the entire length of column Label should indicate the source, date of collection and type of resin Sample quantity should be sufficient for different tests. About 500 ml. for one type and 1000 ml for MB is sufficient

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Resin commissioning.
Cleaning

& inspection of vessel. Column testing or hydrotest of vessel Checking pressure drop with & without resin. Resin charging in vessel Backwash & checking resin bed height. Conditioning of resin before use. Double regeneration.

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Resin testing.