Hi-strength Hypo

Introduction

Calcium Hypochlorite is an inorganic compound marketed as bleaching powder. This compound is more
stable than Sodium Hypochlorite (liquid bleach) due to higher percentages of available chlorine. Calcium
Hypochlorite is available in two forms one is normal bleaching powder and another one is high strength
bleaching powder. Normal bleaching powder consists of 35-40% available chlorine whereas high
strength powder consists of 68-70% available chlorine. This hi – strength hypo is used as sanitizing agent
to treat water in swimming pools.

Production process (At client site)

Production process consists of 4 major steps

1) Milk of Lime (MOL Preparation)

2) Chlorination Reaction
3) Filtration
4) Drying

MOL Preparation: MOL of concentration 175-280 gpl is prepared by mixing measure quantities of raw
water + mother water + hydrated lime + quick lime. Quick lime and mother water is added to reduce the
viscosity of finally prepared MOL. Otherwise MOL cannot flow freely. MOL made out of pure hydrated
lime is less viscous only at lower concentrations. But this concentration cannot be used for production
process as it affects the quality of the product. Another advantage of adding mother water is to utilize
chlorine already present in it.
Chlorination Reaction: It is a 3 stage reaction carried out in 3 different in reactors. In reactor 1,
1.800M3/hr of MOL is fed continuously. Chlorine is fed at the rate of 110-120 kg/hr through dip pipe at
the bottom of the reactor. Reactor 2 is fed with Chlorine at the rate of 200-210 kg/hr and caustic soda is
added at the rate of 630kg/hr. CaCl2 produced in reactor 1 is converted back to Ca(OH)2 in reactor 3
addition of chlorine is based on redox set value. This redox value is based upon excess alkalinity of
Ca(OH)2
Filtration: Rotary vacuum drum filter receives slurry from slurry tank. Vacuum of around 580mm hg is
applied to drum filter by means of vacuum pump. Filtrate (mother water of cal hypo) is removed from
slurry and sent to mother water receiving tank and wet cake with minimum available chlorine (43%-
45%) is formed on the filter cloth. Slurry remaining in the trough of the filter is again taken back into
slurry tank. Water is finely sprayed by means of mist spray nozzles on the wet cake to remove NaCl salt
that is adhering to the cake. Water spray imparts some more moisture to the wet cake. This wet cake is
then taken to a mixer granulator by means of cake belt. Mixer granulator is rotating equipment which is
provided with ploughs arrangement for mixing of chopped wet cake with cal hypo powder which is
coming from recycle hopper. Cal hypo granules are pushed towards 3mm mesh to get uniform granules
before they are sent to dryer.
Drying: Wet granules of cal hypo are dried in fluidized bed dryer by means of hot air, which is supplied
at 135⁰C through air nozzles inside the dryer in its first 3 zones. In the last and 4th zone cold air is passed
through air nozzles to cool down the product to around 55⁰C. Dried powder overflows from dryer to a
vibrating screen to separate cal hypo granules into +0.5mm size and -0.5mm size. Over size is recycled
and undersize is sent to another vibrating screen to separate different sized granules and to obtain
required granular sized product in the size range of 0.8mm to 2.5mm. Over sized and under size
granules from this screen are sent either to compact machine to make granules or recycle hopper.
Exhaust gas containing chlorine, fines of cal hypo powder and water vapor is passed to bag house filter,
which entraps cal hypo and recycles back to recycle hopper. Chlorine containing flue gases is passed
through alkaline scrubber to neutralize chlorine in caustic solution thereby forming Sodium hypo.
There are some issues related to production and analysis of compounds. These issues were categorized
to reaction problem, analysis problem, drying problem and miscellaneous problem. Since there was
problem regarding complete usage of pure hydrated lime as raw material we have made some settling
rate studies on both raw materials.

SETTLING RATE STUDIES

Raw material used in the production process consists of two types of limes Quick lime and Hydrated
lime (more purity). 1 part of quick lime is mixed with 9 parts of hydrated lime to prepare milk of lime
solution which is later chlorinated to get desired product. Company has reported that hydrated lime
solution gets deteriorated after 1hour and turns into unmovable mass. In order to verify information
provided by them we have conducted settling rate experiments for both limes and combination of both
limes.

Hydrated Lime

180 gpl concentrated solution of hydrated lime is prepared. This solution is stirred well for 1 hour at 100
rpm and then stirring is stopped to observe the settlement of solution. After 90 minutes solution started
to settle in the vessel. Similarly another solution of same concentration was prepared and it was stirred
well at 200 rpm for 1 hour. Again settling rate was observed for this solution. In this case also solution
was found to settle after 90 minutes. Same procedure was repeated for other speeds like 300,400 and
500 rpm. For all these cases solution was found to settle only after 90 minutes. Then a fresh solution
was prepared and kept undisturbed for whole night. Next day solution was kept for stirring at 500 rpm
and it stirred well without forming any unmovable mass. After 1 hour stirring was stopped and
settlement studies were done. Solution got settled after 45 minutes.

Quick Lime

180 gpl concentrated solution of quick lime is prepared. This solution is stirred well for 1 hour at 100
rpm and then stirring is stopped to observe the settlement of solution. After 75-80 minutes solution
started to settle in the vessel. Similarly procedure was repeated for remaining speeds 200 to 500 rpm.
For all these cases also solutions were found to settle after 75-80 minutes. Similarly this lime was also
left for overnight settling and same procedure was repeated as done for hydrated lime. Solution got
settled immediately.

Mixture (Hydrated lime 9 parts, quick lime 1 part)

Mixture was prepared according to the desired ratio and concentration of 180 gpl was maintained.
Again this mixture was subjected to same treatment which was done for both limes separately. In this
case solution was found to settle after 90 minutes. This mixture was also left undisturbed overnight and
next morning it was stirred at 500 rpm for 1 hour. This solution got settled after 90 minutes.

Hydrated lime and mixture of both limes didn’t deteriorate even after overnight settling where as quick
lime solution got settled quickly after overnight.

4.3
4.2
4.1
4
3.9
3.8
3.7
3.6 Series1
3.5
3.4
3.3
3.2
3.1
3
0 10 20 30 40 50 60 70 80 90 100 110 120

Fig 1: Hydrated Lime settling curve at 500 rpm

4.2
4.1
4
3.9
3.8
3.7
3.6
Series1
3.5
3.4
3.3
3.2
3.1
3
0 10 20 30 40 50 60 70 80 90 100 110 120

Fig 2: Quick Lime settling curve at 500 rpm

4.25
4.2
4.15
4.1
4.05
4
Series1
3.95
3.9
3.85
3.8
3.75
0 20 40 60 80 100 120 140

Fig 3: Hydrated Lime after overnight settling

4.22

4.2

4.18

4.16
Series1
4.14

4.12

4.1

4.08
0 20 40 60 80 100 120 140

Fig 4: Quick Lime after overnight settling

 4.2

3.8

3.6
Series1

3.4

3.2

3
0 10 20 30 40 50 60 70 80 90 100 110 120

Fig 5: Mixture (9:1) curve settling curve

Client has reported that both limes used were of different particle size and to cross check the particle
sizes of these two materials sieve analysis has been performed.

SIEVE ANALYSIS OF HYDRATED & QUICK LIME

Quick lime particles passing mesh number 80 (Taylor series) and hydrated lime particles passing mesh
number 170 (Taylor series) are being used by industry. They have reported that 99% of hydrated lime
passes through mesh number 170. Individual sieve analysis was done for both limes and we found
deviations from the information provided by industry. Screens with mesh numbers ranging from 60 to
170 were used for analysis.

Hydrated lime

100 grams of hydrated lime was taken and started with mesh number 60. Screen was shaken for 5
minutes and 85% of material on the screen was passed. This passed material was then put on mesh
number 85 and it was also shaken for 5 minutes. Similar procedure was repeated for remaining mesh
numbers and it was found that below 5% of material passed through mesh number 170.

Quick lime

75 grams of quick lime was taken for analysis. Since quick lime consisted of some black stones and other
impurities of bigger size they got screened on mesh number 60. Material which got retained on mesh
number 60 was of around 25-30%. 15% of material got retained on mesh number 85 and rest of it
passed through. This passed through material is used in production process.

From sieve analysis it is concluded that hydrated lime is of less finer size than that reported by industry.
Since problem related to analysis of raw materials, products was reported we have performed similar
tests which were done at client site for both raw material and finished products. These tests were giving
appropriate results. After discussion with analytical division at IICT they have mentioned that for
inorganic compounds titrations is best technique to determine the amount of a particular compound
present. Other online methods are very difficult to handle and there is no consistency/reliability.

Client has requested for online method to determine hypochlorite concentration. In literature it has
been reported that hypochlorite concentrations can be determined using UV-Vis spectroscopy.
Therefore experiments were carried out to validate this method.

DETERMINATION OF HYPOCHLORITE CONCENTRATION BY UV SPECTROSCOPY

A simple, rapid and sensitive method has been developed to determine the concentration of
hypochlorite present in high strength hypo. In this method hypochlorite reacts with potassium iodide in
acid medium and liberates iodine. This liberated iodine bleaches pink color of Rhodamine B and can be
measured in the range of 550-570 nm.

Reagents used:

Sodium Acetate, Hydrochloric acid, Potassium Iodide and Rhodamine B

Procedure:

Hypochlorite solution of concentrations ranging from 200 gpl to 250 gpl was prepared. Since UV
spectroscopy cannot determine concentrations of higher range above solutions were diluted. Dilution
factor of 2000 was used. 1ml of aliquot sample was diluted by adding 1999ml of distilled water. 1ml of
2M HCl and 1ml of 2% KI solution were added to 1ml of diluted hypochlorite solution. This mixture was
gently shaken till it turns into yellow color indicating the liberation of iodine. Then 0.5ml of 0.05%
Rhodamine B solution and 2ml of 1M sodium acetate were added and the mixture is gently shaken for 2
minutes. This mixture is finally diluted to 20ml with distilled water.

Sample prepared from above method is then put into UV cuvette and in other cuvette distilled water is
filled which acts as blank. Then UV scan takes place and peak for hypochlorite is generated at
wavelength range of 550-570nm.

Calibrated curve was developed for known concentrations in order to determine concentration of an
unknown sample.
 3

y = 0.0124x - 0.4687
2.5
R² = 0.9057

1.5 Series1
Linear (Series1)
1

0.5

0
200 210 220 230 240 250

Calibration Curve

This method is consistent only for lower concentrations. The same has been said by our analytical
division and they suggested that iodometry is the best method to determine hypochlorite
concentration.
There are some problems related to chlorination reaction. For reactions we have used only hydrated
lime to prepare MOL. Chlorine was supplied in some excess quantity than required and condenser trap
was used. Purpose of this trap is not allowing chlorine escaping from the reactor, so that more chlorine
will be present for the reaction. By this we achieved better available chlorine percentage in reactor 1
and reactor 2.

MOL Conc Cl2 flow rate % Avl Cl2 - 60 NaOH Water Cl2 flow rate 90 120
30min min added (g) (ml) min min
180 gpl 12.2 g/hr 9.18 15.1 NA NA
9
180 gpl 12.2 g/hr 10.89 14.8 NA NA
9
180 gpl 12.2 g/hr 8.17 14.9 NA NA
6
180 gpl 9.2g/hr (but 9.48 14.6 24.5 70 17.5 g/hr (but
excess is sent) excess is sent)
180 gpl 9.2g/hr (but 6.51 14.0 23.1 52.5 17.5 g/hr (but 17.0 23.3
excess is sent) 8 excess is sent) 7 6
180 gpl 9.2g/hr (but 6.34 13.8 23.1 52.5 17.5 g/hr (but 19.3 24.2
excess is sent) 8 excess is sent) 6 3
180 gpl 9.2g/hr (but 7.42 14.8 18.8 43 17.5 g/hr (but 18.3 24.6
excess is sent) 2 excess is sent) 5
180 gpl 9.2g/hr (but 8.15 14.2 18.8 43 17.5 g/hr (but 19.3 23.8
excess is sent) 5 excess is sent) 8 4
180 gpl 9.2g/hr (but 7.39 13.7 25.32 57.5 17.5 g/hr (but 19.1 23.9
excess is sent) excess is sent) 1