Water Chemistry Water Sources - MAGICHOMEpds.magichome.co.kr/board/encoss/[2]Korea Training...
Transcript of Water Chemistry Water Sources - MAGICHOMEpds.magichome.co.kr/board/encoss/[2]Korea Training...
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Welcome TEAM Korea Tech
Discussion on
TULSION RESIN forWater and special application
By
Thermax Limited - India
South Korea South Korea
World Water Scenario• Three quarters of earth is filled with water
• Estimated water ~ 1.3 X 10 9 km3
• 97.5 % constitute the Ocean (saline water) which is unfit for use.
• Out of 2.5 %, major portion locked in glacier.
• Only 0.5 % is available for human use.
10 countries share 60% of the reserves,
while 29 (in Africa, and the Middle East)
face chronic shortages
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Topics for DiscussionTopics for Discussion� WATER CHEMISTRY
� DIFFERENT TECHNIQUES OF WATER
TREATMENT
� TYPES OF ION EXCHANGE RESIN
� APPLICATIONS OF ION EXCHANGE RESIN
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Water Chemistry • Source• Impurities• Method of Measurement• Units of Measurement• Typical Analysis• Interpretation• Checking of analysis
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Water Sources1.RAIN2.SURFACE3.UNDERGROUND4.SEA
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Water Impurities1.SUSPENDED /
DISSOLVED
2.INORGANIC
3.ORGANIC
4.GASEOUS
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Carbon DioxideTurbidity & SiltAnionicCationic
Oil & corrosion products
Organic matter
Bacteria & PlanktonSilicate &Manganese
Micro OrganismPhosphate Iron
Colloidal SilicaChloride Ammonium
Organic MatterSulphate Potassium
ChlorineColorHydroxideSodium
Methane OxygenOther Suspended Matters
CarbonatesMagnesium
Hydrogen SulphideMud , Dirt and BicarbonatesCalcium
GaseousNonionic and Un-dissolved
Ionic and Dissolved
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Water parameter and its problems
OrganicsCOD (ppm)
OrganicsBOD (ppm)
SilicateSilica (ppm)
SulphateSulphates (ppm)
ChloridesChlorides (ppm)
CO3, OHP - Alkalinity (ppm)
OH, CO3, HCO3M-Alkalinity (ppm)
Dissolved solidsConductivity (ms/cm)
Total dissolved solidsTDS (ppm)
Acidity, AlkalinitypH ( 0 - 14)
Suspended, Colloidal MatterTurbidity NTU
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Units of Measurement• ppm = mg / ltr = gm / m 3
• All parameters in resin applications are measured i n ppm as CaCO3.
• All Chemical react in their equivalent weight.Conversion to CaCO 3
– CaCO3 Eq. Wt. = 50– e.g. ppm of ion in water (71 ppm Cl)
Eq. Wt. (35.5 Eq. Wt. Cl)– ppm as CaCO 3 = Gram eq of ion x 50 ppm as CaCO 3
(Gram eg of ion = Weight of substance ÷÷÷÷ Eq. Wt)
– (71ppm Cl) = 100 ppm as Ca CO 3.
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How to Check Analysis ?• Cation - Anion balance
–Total Cations = Total Anions
–pH Alkalinity e.g. OH or P alkalinity is above 8.2 pH
•
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Why Water Analysis?Water analysis serves following functions
1. Anticipation of problem.
2. Diagnose the problem.
3. Evaluate a change in water treatment.
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Parameters
Conductivity meter. Expressed as micromho/cm
corrosion tendency increases.
2. Conductivity
1. pH paper2. pH indicator
solution.3. pH meter
pH varies accordingto acidic or alkalinecontent. water showscorrosive or scaling tendency.
1. pH
METHOD OF ANALYSIS
SIGNIFICANCEPARAMETER
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Parameters contnd….
Titration with EDTA soln. Expressed in ppm as CaCO3
Chief source of Types : Ca,Mg and total. scale in pipe lines etc
5. Hardness
alkalinity. Analysed after titration with std. acid. Expressed in ppm as CaCO3
Combines with divalent Types : p & m
4. Alkalinity
• Gravimetric analysisDeposits in the water line, heat exchanger etc
3. Suspended solids
METHOD OF ANALYSIS
SIGNIFICANCEPARAMETER
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Parameters
Analysis onColorimetric spectrophotometer
Evaluation of phosphate levels in cooling water. Classified as ortho, poland total phosphates
7. Phosphates
Titration with AgNO3 with chromate indicator, expressed in ppm as chlorides.
Adds to solid content & increase corrosive character of water.
6. Chlorides
METHOD OF ANALYSIS
SIGNIFICANCEPARAMETER
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Parameters
Colorimetric analysis on spectrophotometer. Expressed in ppm as SiO2.
Very hard silicate scale are formed.
9. Silica
Colorimetric analysisspectrophotometer.
expressed in ppm as CaC03.
Adds to solid content & combines with calcium on to form calcium sulfate scales.
8. Sulfates
METHOD OF ANALYSIS
SIGNIFICANCEPARAMETER
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Parameters
Titration with FAS activity. or with chlorotexreagent.
Chlorine demand & biocidal12. FRC
Titration with EDTA with dithizone indicator .
Evaluation of our treatment program.
11. Zinc
Colorimetric analysis On Spectrophotometer
Expressed in ppm as Fe.
Discoloration of water. Deposits in low velocity area and inpipelines
10. Iron
METHOD OF ANALYSIS
SIGNIFICANCEPARAMETER
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SamplingThe sample should be
Representative
Sufficient in quantity
Properly packed and labeled
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Sampling
1. Collect sample in previously sterlised
and closed bottles or containers.
2. Fill sample without rinsing.
3. Sample quantity should be minimum
250 ml.
4. Sample should reach lab within 24 hrs.
5. Label the sample properly.
Sample forAnalysis
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Different Techniques of water Treatment. ????
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Different Techniques Of Water Treatment• Pre-treatment Coagulation ,Chlorination
• Filtration: Sand Filter, Activated Carbon Filter etc.
• Membrane
• Thermal
• Ion exchange
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Different Techniques contd…..
Pretreatment:Extra Hardness by Precipitation� Chemical Coagulation/ Chemical
Precipitation– Hardness and alkalinity removal by
lime soda process (hot or cold)– Iron removalRemoval of Suspended solids
Inorganic Coagulant :# Alum, Iron Salts, etc.# Organic flocculent :-Cationic, Anionic, Nonionic, Polyelectrolyte
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Different Techniques Contnd....Suspended solids
removal contd ….� Gravity settling� Filtration
Different Media :- Sand, Anthracite- Activated Carbon- Polymer Bead- Multimedia Filters- Iron Removal Filters
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Different TechniquesDissolved solids1. Membrane technique Electro dialysis & Reverse
Osmosis
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2. Thermal Desalination
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• A Ion exchange resin is a Insoluble solid polymer having exchangeable ions on which reversible interchange of ions between a solid (IXR) and a liquid takes place.
• A reversible stoichiometric process. Every ion which is removed from the solution is replaced by equivalent amount of another ion of same sign.
• After the ion exchange, the exchanger material can be brought back to original form by suitable reaction, called regeneration.
WHAT ARE ION EXCHANGE RESIN?
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Ion ExchangersInsoluble solid material carrying exchangeable
cations or anions
WAC SAC
Cation Exchange
WBA
Type I Type II
SBA
Anion Exchange
Ion Exchange Resins
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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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Cation Resin Manufacturing
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Weak Acid Cation Manufacturing..
• Polymerisation of methacrylic acid and DVB yield a weakly acidic cation exchanger
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Weak Base & Strong Base Anion Manufacturing..
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Type I & WBA
CH3OCH2ClCHLOROMETHYLETHER
N(CH3)3/Catalyst
CH-CH2-CH-CH2-
-CH-CH2CH-CH2
CH2 N(CH3)3 Cl
-CH-CH2
CHLOROMETHYLATED BEADS
CH-CH2-CH-CH2-
CH-CH2
CH2CL
Styrene
CH=CH2
+
CH=CH2
CH2=CH2
DVB
N(CH3)2/Catalyst
CH-CH2-CH-CH2-
-CH-CH2CH-CH2
CH2 N(CH3)2Cl
Weak Base Anion Strong Base Anion
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Anion Type II
-CH-CH2
Styrene - DVB Copolymer
CH-CH2-CH-CH2-
CH-CH2
NCH3CH2OH (CH3)2/Catalyst
CH3OCH2ClCHLOROMETHYLETHER
-CH-CH2
CHLOROMETHYLATED BEADS
CH-CH2-CH-CH2-
CH-CH2
CH2CL
-CH-CH2
TYPE II RESIN
CH-CH2-CH-CH2-
CH-CH2
CH2 NCH3CH2OH (CH3)2
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Resin structure: Cation
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Structural classification• Since about 1935 organic ion exchangers have been
developed in large scale. Contrary to inorganic exchangers their properties can be varied in a much wider range due to the possibilities of polymer chemistry.
• In general the organic ion exchangers consists of a polymer matrix with functional groups. These functional gro ups may be part of the organic monomers or are introduced by o ther means. The final material has the properties of a r esin and, as a consequence, organic ion exchanger are often design ated as ion exchange resins .
• ON STRUCTURE BASIS IT HAS BEEN CLASSIFIED IN TWO TYPES GEL AND MACROPOROUS
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What is Macroporous resin ?• Also referred to as Macro-reticular resins. • Manufactured using a solvent process that
leaves a network of pathways throughout the beads.
• This sponge like structure allows the active portion of the bead to contain a high level of DVB cross -linking without affecting the exchange kinetics.
• There is an increase of approximately 30-40 % in porosity, which may results in proportionate decrease in exchange capacity due to lowering of the actual exchange sites.
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Gel resins are homogenous cross linked polymers with exchange sites distributed evenly across the bead. The amount of DVB crosslinking used during the synthesis of a bead determines the relative strength of the bead. These resins generally have higher operating efficiency and cost less
What is Gel type resin ?
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Gel and Macroporous structure
WATER
(Moisture)
GEL
Macro porous
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Properties of Tulsion IXR
1. Particle Size2. Effective Size3. Uniformity Coefficient4. Moisture5. Swelling6. Total Exchange capacity7. Kinetics 8. Bulk Density9. Stability
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Properties of Ion Exchange Resins1. Particle Size :
Purely hydraulic and kinetic influence on the ion e xchange process. 0.3-1.2 m size is satisfactory for industr ial applications
0.3mm 1.2mm
2. Effective size = Sieve (mm) on which 90% of beads a re retained.
3.Uniform Coefficient = ratio of sieve size on which 40% retainedto the sieve size on which 90% maintained. .
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4. Moisture Content :It is bound water related to cross linking. About 45 - 55 °C depending on type of resin. Gives valuable information on resin under use
WATER (Moisture)
Properties of Ion Exchange Resins
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5. Swelling :� It is volume change due to change in surrounding
medium.� Depends upon medium, resin matrix.� Ionic group present and type of counter ions� e.g. SAC Na and H form
→→→→←←←←
Form Na Form H
Properties of Ion Exchange Resins
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6. 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.
Properties of Ion Exchange Resins
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7. Kinetics (speed of exchange reaction) :It is influenced by cross linking, functional groups, particle size, properties of the influent and temperature.
8. Bulk Density: Bulk density, shipping weight, true wet density•The bulk density is the weight of wet resin per unit volume. This de nsity is measured in a calibrated glass column after back washing the resin, allowing it to settle and draining off the water. T his density is specific for each resin and is dependent on the type of resin an d ionic form. For each wet resin, Thermax has set a value of bulk density, called shipping weight.9. Stability : During service and regeneration resin is subjected to expansion and contraction. Oxidizing agents attack the resin. There is mechanical attrition. All these influence resin life and economics of operation
Properties of Ion Exchange Resins
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Role of Ion Exchange Resin
• Strong Acid Cation : Removes all cation
• Strong Base Anion : Removes all anion
• Weak acid Cation : Remove hardness associated with Alkalinity
• Weak Base Anion : Removes Organic Acids and FMA (Cl, SO4 & NO3)
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Different application of Ion exchange technique.
- Water Softening. - Demineralization.- CPU - Nitrate Removal- MEG - Heavy metal removal- Sugar - Bio Diesel- Nuclear - Brine
Decalcifications
- Pharma-resin
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1.SOFTENING By TULSION Resin
Nacl
CaCO3
MgCl2Water
SO3Na +
Regenerated resin
SERVICE CYCLE
Na cl
RegenerantCa/Mg +
Exhausted Resin
Ca/Mg +
Na cl
Na2CO3
2NaCl
EffluentExhausted Resin
SO3Na
Regenerated resin
CaCl2MgCl2
NaCl
Effluent
Regeneration
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Tulsion Resins for Softening
Tulsion ® T 40 Tulsion ® T 42
Softmax
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SO3H +
Ca ) HCO3Mg) ClNa ) SO4SiO2Regenerated Cation Exhauted Cation
Ca
SO3 +Mg
Na
H2 ) CO3H) ClH2 ) SO4H2 )SiO3Cation Effluent
CH2NH(CH3)3 OH+
Regenerated anion
H2 ) CO3H) ClH2 ) SO4H2 )SiO3
Cation Effluent
CH2NH(CH3)3
Exhausted Resin
CO3ClSO4SiO3
H2O
2. DM Service cycle
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Regeneration of cation in DM
Regeneration of Anion
Ca
SO3 +Mg
Na
HCl
Exhauted Cation
SO3H +
Ca Cl2MgCl2NaCl
CH2NH(CH3)3
Exhausted Anion Resin
+ NaOH
CO3ClSO4SiO3
CH2NH(CH3)3 OH+
Regenerated anion
Na2CO3
NaClNa2SO4
Na2SiO3
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Tulsion Resins : There are 500 Types of resin
Tulsion T 42 Tulsion 52Tulsion T 50Tulsion T 56MP
Cations Tulsion A 23 Gel, Tulsion A 27MP
Strong Base Anion Type I
Tulsion A 36MP, Tulsion A 36 gel
Strong Base Anion Type II
Tulsion A 2XMP,Tulsion A 10 XMP, Tulsion A 8XMP
Weak Base anion
Tulsion Resins
TypeTulsion Resins
Type
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3. What is Condensate Polishing ?(CPU)• The term 'condensate purification' is normally
applied to the treatment of condensed steam from turbines and processes operating in the power, petrochemical chemical and other industries
• Treatment StandardsSodium : less than 5 µg/l as Na+Silica : Less than 5 µg/lConductivity : Less than 0.1 µs/cm at 25 0CIron : total iron < 5 µg/lCopper : Total copper < 2 µg/l
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Why is Condensate Polishing Required ?
• Traces of soluble impurities present in the feed water entering a high pressure boiler can be concentrated within the system
– The degree to which this occurs depends on the design of boiler, heat flux, oxide thickness at heat transfer surfaces, and the level of insoluble impurities
• In a once-through type of boiler all the water entering a tube is evaporated in a single pass and salt concentration occurs at thewater/steam transition point.
• The result of these concentration mechanisms is that there is a risk of corrosion of boiler tubes by ions such as chloride and sulphate, and if failures occur the economic penalties are very severe.
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Why is Condensate Polishing Required Contnd…. ?• In once-through boilers operating under supercritical conditions, i.e.
such that the critical pressure and temperature is exceeded and a single phase fluid exists rather than two phase water/steam conditions all the impurities in the boiler fluid will be present as the fluid enters the turbine.
• Consequently, there is a risk of substances depositing within the turbine. At the temperatures and pressures involved this includes metallic elements like copper and iron which have an appreciablesolubility under the boiler conditions which reduces rapidly as the fluid passes through the high pressure section of the turbine and can lead to the formation of hard, tenacious deposits(CURD) , resulting in deterioration in output from the turbine.
• It also minimizes consumption of make-up water. • It is also applied if the risk of contamination of return condensate is
persistent.
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Impurities Removed by Condensate Polisher…..• Corrosive Impurities:
– Oxides of iron, copper and nickel are the major cor rosive products Cartridge or pre-coat filters can be used for filte ring
• Dissolved Salts– Sometimes due to leakage of cooling water the impur ities
caused by dissolved salts arise – For low-contamination levels mixed-bed ion exchange rs are
commonly used. – Separate cation and anion exchangers can be used on ly
when there is higher level of mineral contamination .
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Factors Affecting The Performance Of Condensate Purification Plant
• Flow rate• Regeneration procedures and conditions• Composition of water to be treated (Inlet
water)• Quality and quantity of treated water to be
produced
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Cycle Termination Is Depending On Following Parameters
• High pressure drop across the resin bed
• High cation conductivity if Cation tower precede MB .
• High effluent silica leakage from MB.
• Total volume of condensate treated (OBR)
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CONDENSATE FLOW DIGRAM
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CONDENSATE POLISHING
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Tulsion ® Resins For CPU
• Tulsion ® T 50 Tulsion ® A 21• Tulsion® T 52 Tulsion ® A 21
MP• Tulsion ® T 42 MP
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4.MEG What is MEG?
Mono-ethylene Glycol (MEG) is a fiber intermediate product. Major raw material for the manufacture of polyester fiber, filament and yarn.
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pH adjustmentCycle water ���� SAC���� DGT ���� WBA
EO Gas Scrubber Stripping Column
GlycolAbsorptionColumn
DI Unit= SAC+ WBA+ CO2 Removal Unit
Evaporator
Drying Column
MEG Conc
NaOH
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Measurement of MEG Purification• Improvement in pH value . Improvement in Conductivity• Improvement in Transmission
>99> 95> 922 -56.5 – 7.8Outlet
99- 10092 - 94 75 - 8075 – 100 3.4 – 3.5Inlet
350 nm275 nm225 nm
Transmission %ConductivitypHSample
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TULSION Resins in MEG Purification• Tulsion T 56MP
•TEC = 1.7meq/ml.in Hydrogen form.•Macroporous catalytic grade•Can take Cations associated with organic acids.•Good Regeneration efficiency.•Regeneration by HCL •Reg. by 4 - 6 % HCl•High operating capacity. pH range 0 - 14•Max. op. temperature 80 °C•Swelling Na --> H 7 %
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TULSION Resins in MEG Purification• Tulsion A 8XMP HP
•TEC = 1.3 meq/ml.in free base form.•No salt splitting capacity in OH- form.•High reg. efficiency.•Reg. by 120% of stoichiometric qty.•Reg. by 1-5% NaOH•High operating capacity. pH range 0 - 9•Max. op. temperature 80 °C•Swelling OH Cl 18 %
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5.Brine Decalcification
It’s a ion exchange process in which hardness from brine is removed to the required level.
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Tulsion CH 90 Tulsion CH 93
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Critical Impurity limits in Brine Decalcification
• Cationic impurities Ca2+, Mg2+Present in all brines Harmful > 20 ppb
• Sr 2+ Common in rock salt. Harmful if Sr > 100 ppb
• Ba2+Common in rock salt. Harmful if Ba > 500ppb
• Al 3+Common in rock salt. Harmful if > 100 ppb,
• SO42+ Common in rock salt. Harmful if > 10g/l
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6. Glucose DeashingLiquid glucose (LG) and dextrose are obtained from starch,
which in turn is derived principally from maize. Starch is also produced from potatoes, rice, taro etc. When starch is hydrolyzed with mineral acids or enzymes, it is converted to glucose. This glucose contains objectionable impurities such as ash, color bodies and proteinaceous materials. In order to meet specifications laid down by many end-users of LG / dextrose, it is necessary to remove these impurities. Normally glucose is supplied as liquid glucose having concentration of 85 % w/w while dextrose is supplied as white crystalline powder.
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GLUCOSE SYRUP 85 % W/W
FILTER ONCE USED CARBON
STARCHSLURRY
ACID / ENZYME HYDROLYSIS
“BREAK POINT”TANK
Na2CO3
CENTRIFUGE
I CARBON AT 60 °°°°CFILTER
SPENT CARBON DISCARDED
T42GEL
SAC
A 2X MP
WBA
II CARBON AT 60 °°°°C
VACUUM EVAPORATION
PAN BOILING TO CRYSTALLIZE DEXTROSE
MARKET
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Tulsion ® Products for Glucose Deashing
• Tulsion T 42• Tulsion A2XMP• Tulsion T 46MP• Tulsion A 2XMP-R• Tulsion T 52
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7. Nuclear
A nuclear power plant is much similar to a coal fir ed thermal plant except the way heat is produced to raise steam. At the heart of a nuclear power plant is the fission reaction in the nuclear fuel,usually uranium, takes place in the reactor core. T o be simplistic, in a nuclear fission, a neutron hits the nucleus of an atom of the uranium fuel and splits it, in which two or three n eutrons are released and used to cause fission in other uranium atoms. Fission of a single atom of uranium yields energy e qual to 200 MeV (million electron volts) in comparison to only 4 eV in the oxidation of one carbon atom. Therefore, on equal w eight basis the total energy from the nuclear fission of 1 tonne of uranium is about as much as that produced from 2.5 million ton nes of coal combustion.
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Tulsion ® Products for Glucose Deashing
• Tulsion® T 46
• Tulsion® A 33
• Boron Enrichment resin
• Chelating Resin
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8. Nitrate Removal• Nitrates have no detectable color, taste or smell at the
concentrations involved in drinking water supplies, and they do not cause discoloration of plumbing fixtures, so they remain undetectable to our senses. Nitrate removal processes must be either foolproof or include extensive monitoring of the treated water to detect breakthrough or determine the need for regeneration.
• Infants are particularly susceptible to nitrates because their digestive systems do not operate in the exact same manner as adults. Nitrates are converted by bacteria in the stomach of infants to toxic nitrites. At levels that would not cause harm to adults, nitrates can cause methemoglobinemia in infants, a condition also known as "blue baby" syndrome.
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Nitrate removal ResinTulsion ® A 62MPThe term "nitrate selective" refers to resins that retain nitrates more
strongly than any other ions including sulfates. A variety of functional groups can and have been placed into anion exchange resins that are nitrate selective. The affinity relationship for ni trate selective resins in drinking water is
Nitrate > Sulfate > Chloride > BicarbonateFunctional Group : Quaternery AmmoniumParticle Size : 0.3 to 1.2 mmpH range : 0 to 14
Regenerant : NaCl
Use Industrial water and Domestic waterOutlet Limit < 1 ppm.
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9. Heavy Metal removal• Iron Removal Resin
From : Sulphuric acid
; Water: Solvent
• Copper Removal from PCB waste.• Zinc Removal rayon manufacturing.• Nuclear heavy metal removal from reactor water.• Barium , Lead • Arsenic• Gold• Chromium from plating Industry
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There are mainly four steps for bringing resin in process
1. Backwash
2. NaOH injection
3. Slow Rinse
4. Fast Rinse
5. Service
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Back Washing
Back washing is done for :
� Loosening the bed
� Re classifying the bed
� To remove dirt and filtered matter
By back washing, more uniform distribution of fluid is obtained in subsequent down-flow operation.
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Back WashingInjecting water in upward direction to expand the bed to about 50%. DM water used for backwash. Can carry out for 15-20 minutes Service Flow
Outlet
Nozzle Plate
Resin Bed
Before Backwash After Backwash
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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.
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Regeneration by Co-flow
Regenerant inlet.
Regeneration outlet.
RESIN BED
Service inlet
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Counter - Current regeneration.(CCR)
Service inlet
Regeneration inlet.
Regeneration Outlet.
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•Slow Rinse:It is extended regeneration. Hence at regeneration flow rate generally by 2-4 BV of water – DM water
Fast Rinse :To remove traces of regenerant.Done at service flow rate. – DM water
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• TROUBLE SHOOTINGSouth Korea
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Troubleshooting• Ion exchange units may experience problems during
operation• For effective troubleshooting consideration should
be given to the following areas:-– Flow rates– Pressure drop– Resin– Backwash :- Pressure drop– Regeneration :- Concentration, Quality– Water quality :- Ion concentration (Ionic load)– Design criteria :- Original design and operating cond ition
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Troubleshooting• Problems generally encountered
–High pressure drop –Decrease in pressure drop–Reduction in capacity (Output)–Poor Quality of treated water
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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 ShootingMajor 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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MBService/Alkali/Down/
Alkali Rinse
Regenerant Effluent
Acid flow/Acid RinseTreated water
Free BoardResin bed Anion and
Cation
Distributor
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THANK YOU
(NOT)
THE END