a-MDEA Analytical Procedure

Schedule of Analysis
Weekly Analysis a-MDEA
a-MDEA CO2 loading
Chloride Fe Lean Semi lean Rich
Specification 25 ppm 25 ppm
3-10 20-30 32-50

Result 7.1 7.5 1.80 29.1 43.15

Daily
Concentration of a-MDEA and Piprazine once a day in reflux sample.

2.10 Determination of aMDEA concentration.

aMDEA solution is used to remove CO2 from the process steam. The
concentration of aMDEA need to analysed for % MDEA and % Piprazine on a
regular interval. Two methods are described as under.

(A) Manual Titration Method:

2.10.1 Reagents
a) 1 N standard HCl
b) Mixed Indicator 100 mg methyl orange in 100 ml D M water + 500 mg of
indigo sulfonic acid (sodium salt of indigo carmine) in 50 ml DM water.

2.10.2 Procedure
Weigh accurately up to fourth decimal about 2 - 3 grams of refluxed sample
and transfer it into a conical flask containing 50 ml of water. Titrate the
solution with 1 N hydrochloric acid to the mixed indicator end point.

2.10.3 Calculation
(1) When concentration of piperazine is known

Or

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 For W = 2.05 g

(2) When ratio of MDEA to Piperazine is known.

Where
BR = Volume of standard HCl solution.
N = Normality of standard HCl solution
F = Factor for standard HCl solution
W = Weight of sample taken
Cpip = Concentration of the piperazine in MDEA
MW MDEA = 119.16 (molecular weight of MDEA)
EMDEA = 119.16 (equivalent weight of MDEA)
MW Pip = 86.14 (molecular weight of Piperazine)
EPip = 43.07 (equivalent weight of Piperazine)
R = Ratio of MDEA to Piperazine.

(B) Auto titrator method:

Concentration of MDEA and Pip can be titrated with auto titrator in single titration
run. Take 2 ml of refluxed MDEA solution in 150 ml beaker, Add approximately 75
ml of DM water. Insert pH electrode and start stirring with magnetic starrer. Enter
the weight, and titrate with 0.5 N HCl solution. During the titration two endpoints
are obtained, Ep1 and Ep2. Since piprazine is a dibasic compound, it shows two
point of inflection during the titration, and MDEA is monobasic, it shows one point
of inflection. The solution is a mixture of both piprazine and MDEA, the first point
of inflection is common for half the value of piprazine and total value of MDEA,
where as second point of inflection will be absolutely for rest half of the piprazine
value.

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 Formula and its interpretation:
Writing the formula in Methrom titrator has some significant way.

In this equation,
R1 = piprazine concentration % w/w
EP2 and Ep1 are the two endpoint values
CV01 = exact Normality of acid (Factor of HCl)
43.07 = eq wt of piprazine
C00 = weight of sample taken for the titration.
R2 = some value like

Where,
R3 = concentration of MDEA % w/w
R2 = empirical value (double the value of first end point, minus value of
second end point.
Cv01 = exact Normality of acid (Factor of HCl)
C00 = weight of sample taken for the titration.
To understand the exact formula,
R = Ep1 2(Ep2-Ep1) and

and,

2.11 Determination of chloride ion in aMDEA. (mercuric thiocyanate method )

2.11.1 General
In this method, solutions of ferric ammonium sulfate and mercuric thiocyanate
are added to the sample. The chloride ion reacts with the mercuric thiocyanate
to produce thiocyanate ion which in turn combines with ferric ion to form red
ferric thiocyanate. The intensity of the colour which is proportional to the
concentration of chloride ion is measured spectrophotometrically at a wave
length of 460 nm.

2.11.2 Reagents
i) Ferric alum solution

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 Dissolve 5 grams of ferrous ammonium sulfate [Fe(SO 4)2.(NH4)2SO4.
6H2O) in 20 ml of water. Add 38 ml of concentrated nitric acid ( sp.gr =
1.42) and boil to oxidize the iron and remove the oxides of nitrogen. Dilute
to 100 ml with halide free water.
ii) Mercuric thiocynate methanol solution (3 g/liter)
Dissolve 0.3 g of mercuric thiocyanate [Hg(SCN)2] in 100 ml of methanol.
Store in amber coloured bottles. Allow to stand for at least 24 hours before
using. A slight precipitate may form and may settle out after the 24 hour.
Care must be taken so that this precipitate is not re suspended when using
the reagent. Only the clear, supernatent liquid must be used.
iii) Sodium chloride standard solution (1 ml = 0.01 mg of chloride)
(A) Stock solution ( 1 ml = 1 mg of chloride).
Dissolve exactly 1.649 g of sodium chloride primary standard (dried at
600C for 1 hr.) and make up to 1 lit with DM water.
(B) Chloride solution (1 ml = 0.01 mg)
Dilute 10 ml of stock solution to the one liter volume.

2.11.3 Procedure

Preparation of calibration curve and sample analysis

Since chloride ion is a common contaminant, extreme care is required in
conducting the analytical determination. All the glass wares must be cleaned
first with hot nitric acid (1+20) and then with silica free water.

For calibration curve, take appropriate volumes of standard chloride solution

to cover the required range. For 1 cm cell the appropriate range of the graph
is 0.005 to 0.25 mg and for 4 cm cell ir is 0.001 to 0.1 mg.
i) Transfer 5, 10, 15, 20 and 25 ml of the standard NaCl solution (1 ml =
0.01 mg of Cl.) corresponding to 0.05, 0.1, 0.15, 0.20 and 0.25 mg chloride
respectively. Add 5 ml HNO3.
ii) For sample, take appropriate volume (5 ml to 10 ml) in previously cleaned
beaker, depending upon the expected concentration of chloride ions, so
that it is within the range of standard curve. Add 5 ml HNO 3 and just boil to
expell out all the CO2 from the sample. Make up to 40 ml approximately by
addition of silica free water.
iii) Add to the sample / standard, successively 5 ml of ferric alum solution and
2.5 ml of mercuric thiocyante solution.
iv) Mix thoroughly and make up to 50 ml by silica free water and allow to stand
for 10 minutes.

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 iii) For reagent blank take the reagents and make up to 50 ml with silica free
warer.
iv) Prepare also sample blank, taking same amount of sample, add 5 ml
HNO3 boil and cool, add all the reagent omitting mercuric thiocynate. Make
to 50 ml with silica free water.
v) Set zero absorbance with reagent blank, measure the absorbance of the
sample blank and sample. Subtract sample blank's reading from the
absorbance of sample if appreciable reading is obtained.
The nature of the standard graph will be curve.
Calculate the chloride content of the sample from the graph.

2.11.4 Calculation

2.12 Determination of iron in aMDEA.

2.12.1 Reagents
i) Buffer solution (pH 4.5)
Dissolve 200 g of ammonium acetate and 250 ml glacial acetic acid to 500
ml of water and make up to one liter. Confirm the pH and if required adjust
to pH 4.5 using glacial acetic acid.
ii) Hydroxyl amine hydrochloride
Dissolve 10 g of hydroxyl amine hydrochloride (NH2OH.HCl) in DM water
and dilute to 100 ml with DM water.
iii) O - Phenanthroline solution
Dissolve 1 g of 1,10-phenanthroline monohydrate in one liter of methanol.

2.12.2 Procedure
i) Take two 50 ml volumetric flask. Add appropriate volume of aMDEA
sample in one volumetric flask. Add 10 ml D M water in another 50 ml
volumetric flask.
ii) Transfer 10 ml of buffer solution and 2 ml hydroxyl amine hydrochloride
solution in each flask. Swirl the flask to expel CO2.
iii) Transfer 2.0 ml of ortho -phenathroline solution in flask and make up all the
flask up to mark with D M water.
iv) After 15 min. determine the absorbance of sample at 515 nm after setting
zero with reagent blank.

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2.12.3 Calculations

Where
Ab = Absorbance for sample
F = F actor from Standard graph. i.e. mg iron per unit absorbance.
V = Volume of sample taken for colour development in ml.

2.13 Determination of piperazine concentration (Plant sample).

2.13.1 Reagents
i) 1.0 N Hydrochloric Acid.
ii) 0.5 N Sodium Hydroxide.
iii) Iso propanol
iv) Carbon di Sulphide
2.13.2 Procedure
i) Weigh accurately up to fourth decimal about 1.5 g of the sample and transfer
into a conical flask.
ii) Add 50 ml Iso propanol and 10 ml 1 N HCl. Boil the solution for about one
minute to expel CO2.
iii) Add 10 ml D M water. After cooling add phenolphthalein indicator and
neutralise the mixture exactly with 0.5 N NaOH.
iv) Add 2 ml Carbon disulphide and shake for one minute.
v) Zero the burette and titrate with 0.5 N NaOH till the pink colour is reached.
The pink colour must last for one minute.

2.13.3 Calculation

Where
V = ml of 0.5 N NaOH
N = Normality of NaOH
F = Factor for standard solution.
43.08 = Eq. wt. of Piperazine
0.9 = Correction factor for the indicator method.
W = weight of sample in gram

2.14 Determination of CO2 loading in aMDEA solution

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2.14.1 Reagents
i) BaCl2 20% solution in DM water.
ii) NaOH 0.5 N standard solution
iii) HCl 0.5 N standard solution
iv) KOH 40% solution on DM water.
v) Mixed indicator :100 mg Methyl Orange in 100 ml D M water + 500 mg
of Indigo Sulfonic Acid (Sodium salt of indigo Carmine) in 50 ml D M water.

2.14.2 Sample collection

i) Take 200 ml of 40% KOH solution in a 500 ml PVC bottle, wipe out the side
wall with the tissue paper and weigh the bottle, say W 1 gram.
ii) Flush sample point thoroughly, close sample valve. Dip the sample point tube
into KOH solution bottle. Collect the sample by slowly opening the sample
valve with swirling till about 150 to 200 gm. of sample is collected.
iii) Weigh the bottle after sampling, say W 2 gm. Make up the sample to 500 ml by
volumetric flask with DM water.

2.14.3 Procedure
i) Take 20 ml BaCl2 solution for rich aMDEA sample and 10 ml BaCl2 for lean
aMDEA sample in two conical flasks containing 50 ml D M water. Keep both
the flask on a hot plate for boiling.
ii) Add 25 ml diluted samples ( i.e 8 to 10 g) for lean and 10 ml ( 4 to 6 g) for rich
aMDEA in hot BaCl2 solution. Again keep both the flask on hot plate for
boiling, let it boil slowly for 2 to 3 minutes.
iii) Take both the flask from the hot plate and filter the solutions immediately by
vacuum filtration using G - 3 Gooch crucibles.
iv) Wash out all excess KOH and BaCl2 solution using hot DM water.
v) Keep these two crucibles separately in two wide mouth 250 ml conical flasks
and then add 40 ml 0.5 N HCl to each flask. Wait for some time till all the
precipitates are dissolved.
vi) Add 50 ml DM water and 2 -3 drops of mixed indicator in these flasks and
titrate unreacted HCl with standard 0.5 N NaOH using mixed indicator colour
change from violet to green.

2.14.4 Calculation

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(Unit is NM3 / ton of solvent or ml / gram of solvent)
Where
VHCl = volume of HCl taken
VNaOH = volume of NaOH consumed
N = Normality of the standard solutions
F = factor of the standard solutions
W = weight of the samples

2.15 Foam testing for aMDEA solution

2.15.1 Equipment
Spherical diffuser stone: ax536, porous alundum sphere (composite
description for alumina & carborundum) consisting of 86-90 % melted
aluminium oxide.
2.15.2 Procedure
i) Place the diffuser stone in DM water for at least 1 hour.
ii) Before performing the foam test pass air at constant gas flow of 60 liter / hour
through the stone for 10 minutes.
iii) Pour 150 ml of the CO2 free solution into a 500 ml measuring cylinder.
iv) Introduce the diffuser stone, in the solution and sparge it with air at 60 liter /
hour for 5 minutes.
v) Measure the resultant foam height (upper foam level from liquid level).
Following the cessation of sparging, measure the time required for total
breakdown of the foam, or until a so called eye is formed on the liquid
surface.
Note
Premature 500 ml foam level (i.e. the 500 ml mark is reached before the 5
minutes are up), the time taken to achieve this level is taken as the
measurement. Repeat the procedure with three successive samples to ensure
meaningful results.