CCB 4433 REACTOR DESIGN FOR PETROCHEMICAL

TERM PAPER

Group Members
1.
2.
3.
4.

Nur Farhana Ajua binti Mustafa

Nurfarahin binti Burhanuddin
Nuralia Syairah binti Osman
Nurul Fatiehah binti Abdul Halim

15583
15612
15669
15592

Submission Date

: 13TH December 2015

Lecturer

: AP Dr Suzana Bt Yusup

Chemical Engineering Department,

Universiti Teknologi PETRONAS

QUESTION 1

QUESTION 2:
QUESTION 3:

QUESTION 4 by Nuralia Syairah bt Osman (15669)

1. INTRODUCTION
Iodine value (IV)
Iodine value is define as unsaturation of the esters present in the biodiesel and it is
determined by the quantity of grams of iodine that reacts directly with double or triple bonds
between carbon atoms, for each 100 g of biodiesel [1]. While according to [2][3], iodine
value is a measure of unsaturation of the fats and is defined as number of grams of iodine
absorbed by 100 grams of substance. The higher the iodine value, the more unsaturated fatty
acid bonds are present in a fat [2]. In this research, the rate of hydrogenation of palm stearin
fatty acids was described in terms of reduction in iodine value (IV). Fatty acids with low
iodine value (IV<15) are the most difficult to hydrogenate.
Saponification Value (SV)
Saponification value is linked to the average molecular weight of all fatty acids and
represents the quantity in grams of potassium hydroxide required to saponify 1 g of oil [3]
The standard use to identify iodine value and saponification number is
1) JIS K 0070-1992 Test Method for Acidity, Saponification value, Ester value, Iodine
value and Hydroxy value of Chemical products and Unsaponifiables matter
2) ASTM D 5558-95 Standard Test Method for Determination of the Saponification
Value of Fats and Oils
3) ISO 3657: 2002 Animal and vegetable fats and oils Determination of saponification
value
Acid Value
Acid value (AV) is defined as the amount of potassium hydroxide (KOH) in miligram
required to neutralize the free fatty acids in 1 g of the oil [4]. 2-Thiobarbituric Acid Value
(TBA) is defined as the increase of absorbance measured at 530 nm due to the reaction of the
equivalent 1 mg of sample per 1 ml volume with 2-thiobarituric acid [5].

2. METHODOLOGY
Iodine value (IV) in fats/oils
According to [3], the analyses have been conducted according to ISO 3961 standard. Samples
are dissolved in solvent and added with Wijs reagent. After a defined time potassium iodide
and water are added and the liberated iodine are titrated with a sodium thiosulfate solution
(starch as indicator). Results are then expressed in grams of iodine absorbed by 100 g of
sample.

Equivalent Weight of Iodine = 127

Normality of sodium thiosulphate (Na2S203) = 0.1

Saponification number (SV)

The SV of the sample is a measure of the total fatty acids, bonded and not, in vegetable oil or
fat. The analyses have been conducted according to ISO 3657 standard [3]. Samples are
dissolved in solvent and a defined amount of potassium hydroxide is added. After a certain
reaction time the residual potassium hydroxide is titrated with a hydrochloric acid solution
(phenolphthalein as indicator). Results are then expressed in milligrams of potassium
hydroxide used for the saponification of a gram of sample.
Saponification value or number of fat = mg of KOH consumed by 1g of fat.
Weight of KOH = Normality of KOH * Equivalent weight* volume of KOH in litres
Acid Value (AV)
The majority of national and international standards for AV determination in vegetable oils
are based on the acid-base titration techniques in non-aqueous solvents [4]. The new
proposed technique is based on indirect acid base titration using a special reagent.
Procedure [4]

To prepare the titration reagent (1 L), mix 500 cm3 deionized water, 500 cm3 2-PrOH and 7
cm3 triethanolamine. Place about 100 cm3 of the reagent into a conical flask on a magnetic
mixer, add 0.5 cm3 of phenolphthalein solution2 to obtain pink colour of the reagent. Add an
oil test portion of the mass, accuracy 0.2 %, to the reagent. Mix the reagent on the stirrer
until colourless for about 1 min, and then, keeping on stirring, begin titration with 0.1
MNaOH or KOH aqueous solution. The titration is finished at the appearance of the first
permanent pink colour of the same intensity as before adding the sample. The colour is
supposed to persist for 10 s.
Acid number is: Strength of KOH x vol. of KOH x eq. wt of KOH in (mg).

3. DISCUSSION
Use the slurry reactor analysis to evaluate the effects of mass transfer and determine if
there are any mass transfer limitations.
Slurry reactor is multiphase flow reactor in which solid catalyst particles is suspended
in the liquid and the reactant gas is bubbled through the liquid. Hydrogenation of oils or fatty
acids in nickel catalyst is the typical reaction occur in slurry reactor. It is a process which
hydrogen is chemically reacted with unsaturated double bonds present in fatty acids [6].
Multiphase reactions is constrained by the mass transfer limitations which lead to low
conversion rates and undesirable product distribution [7]. Reaction rates in slurry reactor can
be affected by liquid reactants concentration, temperature, partial pressure of the gaseous
reactant, the stirring rate and the catalyst hold-up [8].

In the research of hydrogenation of soybean oil using metal decorated polymeric

membrane by [7], hydrogen gas is dissolved in liquid oil contain solid catalyst to form trans
fatty acid (TFA). The low solubility of hydrogen in oil leads to increased mass transfer limitations
and scarcity of hydrogen at the catalyst surface. Hydrogen mass transfer to the catalytic sites has
been recognized as the major limiting step in the conventional hydrogenation process.
Temperature and pressure are important parameters in reactor design. Operation at higher
temperatures is often desired due to increased reaction rates. However, for the case of
hydrogenation of vegetable oil in a slurry reactor, an increase in temperature increases the rate of
formation of TFA due to decreased hydrogen solubility in oil and an increased hydrogenation rate

leading to hydrogen starvation of the catalyst. Increased hydrogen pressures can be used to
increase the solubility of hydrogen in oil and reduce the formation of TFA.

Another case study is hydrogenation of Palm mid fraction (PMF) over nickel catalyst
have discussed the effect of temperature on mass transfer resistance. Temperature is affecting the
fatty acid composition and formation of trans fatty acids (TFA) in PMF [6]. The reaction
conversion and selectivity has increased with increase in temperature. Besides that, increasing
hydrogenation temperature is reducing the resistance to hydrogen diffusion from hydrogen bubble
to the PMF, The mass transfer coefficient also increase with increasing temperature [6].

Meanwhile, in other research by [2], the hydrogenation of palm stearin fatty acid occur at
high temperature (>423 K) cause the increase of diffusivity in gas phase. In a slurry reactor,
catalyst is keep in suspension and the impeller speed controlled the intensity of turbulence. It was
observed that the intense speed of agitation gives better mass transfer and enhance the reaction.
The effect of mass transfer inside the catalyst pore was negligible. In addition, catalyst particle
size had no effect on the rate of reaction. Hence pore diffusion was deemed to be absent.

REFERENCE
[1]

A. Oliveira Barradas Filho, A. Kardec Duailibe Barros, S. Labidi, I. Moraes Amorim

Viegas, D. Brandes Marques, A. R. Romariz, R. M. de Sousa, A. B. Lopes Marques,
and E. Pereira Marques, Application of artificial neural networks to predict viscosity,
iodine value and induction period of biodiesel focused on the study of oxidative
stability, Fuel, vol. 145, pp. 127135, 2015.

[2]

M. a. Tike and V. V. Mahajani, Kinetics of hydrogenation of palm stearin fatty acid

over Ru/Al 2O3 catalyst in presence of small quantity of water, Indian J. Chem.
Technol., vol. 14, no. January, pp. 5263, 2007.

[3]

G. Toscano, G. Riva, E. Foppa Pedretti, and D. Duca, Vegetable oil and fat viscosity
forecast models based on iodine number and saponification number, Biomass and
Bioenergy, vol. 46, pp. 511516, 2012.

[4]

E. Kardash and Y. I. Tur, Acid Value Determination in Vegetable Oils by Indirect

Titration in Aqueous-alcohol Media, Croat. Chem. Acta, vol. 78, no. 1, pp. 99103,
2005.

[5]

J. Pokorny and a. Dieffenbacher, Determination of 2-thiobarbituric acid value: direct

method - results of a collaborative study and the standardised method, Pure Appl.
Chem., vol. 61, no. 6, pp. 11651170, 1989.

[6]

A. M. Alsobaai, A. M. Al Shaibani, T. Moustafa, and A. Derhem, Effect of

hydrogenation temperature on the palm mid-fraction fatty acids composition and
conversion, J. King Saud Univ. - Eng. Sci., vol. 24, no. 1, pp. 4551, 2012.

[7]

D. Singh, P. H. Pfromm, and M. E. Rezac, Overcoming Mass-Transfer Limitations in

Partial Hydrogenation of Soybean Oil Using Metal-Decorated Polymeric Membranes,
vol. 57, no. 9, pp. 131, 2011.

[8]

E. Santacesaria, M. Di Serio, and P. Iengo, Examples of hydrogenation in semibatch

and continuous slurry reactors, vol. 52, pp. 363376, 1999.