Central Laboratory Standard test Methods

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Doc.Nr.:KRC/CL-STM-4-01 Issued date:

Corporation / Fang - Analysis - Standard

3 - 6011
Boiling and Potentiometric Method to Measure Total Chlorinity in the
Platforming Catalyst
UOP 291 - 76
1. Scope
This method is to measure the total content of chlorine and bromine in the platforming catalyst.
2. General outline of the method
The catalyst shall first be deoxidized with the hydrazine, and then leached with the hot sulfuric acid in
the backflow. Do the electrometric titration to the chloride with the silver nitrate solution.
3. Instruments
Beaker: for the titration, 250 ml, of high shape.
Burette: 10 ml, with the scale of 0.05 ml.
Condenser: of rubber solid type, as shown in the following figure

High-type no-spout beaker

Figure 1 Reflux device

Electrode: glass electrode.
Electrode: of silver - silver bromide and steel billet type. Preparing the electrode shall employ the
middle - grade abluent and cleaning powder to clean the surface of silver or silver bromide electrode
couple, and then wash the electrode in the water; dip the metal tip in the saturated potassium bromide
(KBr). Connect one of the electrodes with the anode of a 1.5 - v dry battery and the other electrode with
the cathode. Switch the polarity of current for many times every several seconds, but it is required to
clean and recoat the electrodes of receptor alternatively every time. If coated properly, the tip of the
electrode of receptor will appear purple. Such color is created due to the light action on the fresh silver
bromide, but it almost has no influence on the electric potential of electrode. Take the electrodes out of
the solution, and wash the electrode with the water, but the newly - coated silver - silver bromide
electrodes can be stored in the KBr solution temporarily. Using such a kind of electrode is because it has
enough susceptiveness and durability.
Filter paper: Schleicher and Schuell NO.597, or the equivalent.
Heating plate: of electric type.
Electrometric titration device: it is a recordable product, one (Metrohm) “electric potential graphical
plotter” is a satisfied product.
Stirring rod: it is used to daub the tetrachlorethylene, and is a magnetic one.
4. Reagents and materials
Unless specified specially, all the Reagents shall comply with the specifications prescribed by the
Analytical Reagent Committee of American Chemical Society, if all the specifications can be met, the
separate regulation need not be made; the relevant water refers to the distilled water.
Silicon carbide crystal;
Hydrazine hydrate: 85%;
Hydrazine hydrate solution: dilute 5 g of hydrazine hydrate to 1 L.
Silver nitrate solution: standard water solution of 0.01 and 0.1 N.
Nitric acid: 7.0 to 7.5N, dilute 200 ml of strong nitric acid to 1 L to make the concentration of diluted
acid of not more than 8N. Cool down the water and stir the water without stop, and then add the strong
acid into the water carefully. The best method is to add the acid in the 600 g ice blocks made of the
distilled water, and then to dilute the solution to 1 L.
5. Methods
Take about 5 g of catalyst, and the weight should be correct to 1 mg; put the catalyst in the titration
beaker with the capacity of 250 ml, and add 20 ml of hydrazine hydrate solution (5 g every litre) and
some silicon carbide crystal in the beaker, and then put the beaker on the heating plate. Heat the
substances in the beaker exactly to boil, and keep the boiling state for 10 min slowly; take the beaker off
from the heating plate, cool it slightly, and add 75 to 100 ml nitric acid of 7.0 ~ 7.5 N. Put the beaker on
the heating plate, and insert an acorn - shaped condenser to make the water flow through the condenser;
turn on the heating plate, if the sample is a fresh catalyst, boil the solution for about 2 hours slowly, if
the catalyst is a used one, it is required to boil the solution for a longer time (see the attached notes); cut
off the power supply and stop heating, let the beaker fully cooled until the temperature of beaker can be
contacted with the hand; disassemble the acorn - shaped condenser, wash the acorn - shaped condenser
with the water and collect the residue in the beaker.
Before the titration of one group of test samples, it is required to titrate the sodium chloride solution
with several ml of silver nitrate solution of 0.1 N to make the electrode in a good state, and then titrate
the test sample with the silver nitrate solution of 0.1 N. Stir the solution quickly during the titration, but
the electrode cannot be exposed to the air. When the titration is to be finished, the titration speed should
be drop from 2.5 ml / min to 1 ml / min; for the chlorides with low content, it is required to titrate with
the solution of 0.01N.
The terminal point of titration is the alternation speed of electric potential Δcmf / Δ ml at this point, and
it is the capacity of titrant at the maximum point. In other words, the titration data can be plotted out,
and the terminal point can be determined from the inflection point of titration curve. If a automatic
recording titrimeter has been employed, the curve diagram can be generated automatically.
In some cases, the used catalyst contains only the chlorine, but also the bromine, and the content of
bromine also can be measured. The employed method is like the above - mentioned. Except that the test
sample can be titrated with the silver nitrate solution, the inflection point of bromide occurs at the point
of - 0.200 V; if the bromide and the chloride exist at the same time, there occur two inflexion points on
the curve; the first one is for the bromide and at the point of - 0.200V, but the second one is for the
chloride and at the point of - 0.150V.
Adopting the fresh reagent to carry out the empty reagent test every time can save the samples, but
according to the same methods employed during the analysis, the empty reagent test shall adopt not
more than 0.1 ml and 0.1N of silver nitrate solution.
If the result is for the composition report, the burning weight loss should be measured according to UOP
275 method.
6. Calculation
The bromide content should be calculated according to the following equation:
(a) Calculate according the received samples:
A  N  7.99
Br, Weight% =
W
(b) Calculate according to the dry ingredients
A  N  7.99
Br, Weight% =
W  (100  V )
The chloride content of the sample can be calculated according to the following equation:
(a) Calculate according the received samples:

Cl, Weight% =
(b) Calculate according to the dry ingredients

Cl, Weight% =
Where,
A = Volume of silver nitrate at the terminal point of bromide titration, ml;
B = Volume of silver nitrate needed by the titration of reagent empty test, ml;
C = Total volume of silver nitrate needed by the bromide and chloride, ml;
N = Equivalent concentration of silver nitrate;
W = Weight of sample, g;
V = Burning weight loss %, measured with the UOP 275 method.
Notes: the new catalyst can be dissolved in 2 hours, and the solution do not have to be completely
limpid, can be may be slightly turbid, but the residual solid particles are not allowed.
The used catalyst is often covered by the coke deposit; therefore, it is very difficult to determine when
the alumina has been dissolved; when the particles coated with the coke is floating in the boiling
solution, most of the alumina has been dissolved, and then let the solution boil for about 1 to 2 hours.
After the solution has been cooled down, crush the particles with the rod, and there shall no sand grains
in the particles. Generally, doing 6 hours of back flow can dissolve almost all the indissolvable catalyst
samples; if the 6 hours of backflow operation cannot dissolve the sample, do the backflow operation for
a whole night. If the sample is hard to treat and it cannot be dissolved in 20 hours, the re - boiling is of
no effect. At this point, the sample should be fully leached with the hot sulfuric acid, and large amounts
of halide compounds will be dissolved in the acid solution. Therefore, the analysis can be kept on.
7. Precision:
The catalyst sample should be measured repeatedly, and for the chloride with the content of 0.7 to 1.5
wt%, the difference should not be more than 0.02%.
Calculated according to the range of average and the logarithm of specified samples, the statistical
standard deviation (esd) shall be:
 Chlorine, Weight%
Type of catalyst Logarithm Range Esd Allowable difference
UOP platforming catalyst 27 0.7 ~ 1.5 0.07 0.021

8. Analysis time:
The total time of every analysis process is between 3 and 20 hours. It depends on the necessary time for
the dissolving or leaching of the catalyst. The fresh catalyst can be dissolved in 3 hours, but the used
catalyst will be dissolved in 6 to 20 hours. The estimated man - hour of every analysis, for a single
sample each time, should be 1.0 hour, but for the group analysis of 6 or more samples, the man - hour
for one sample every time should be 0.5 hour.