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Optimization of the nicotine sulfate preparation from tobacco wastes

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Engineering & Technology, Vol.21, No.8, 2002
·:.;.::;;;.\:·'..

OPTIMIZATION OF THE NICOTINE SULFATE

PREPARATION FROM TOBACCO WASTES

Mahmood M. Barbooti, *Majid S. Radha** &

Shurooq T. Ramadhan **,
Received on: 301912001
Accepted on: 131512002
Abstract
After the leaching of nicotine from tobacco dust by water/ alcohol
mixture (1 :1), the filterate was extracted with chloroform/ hexane
mixture (7.5%) at a ratio of 1:1 (solvent to aqueous) at 400 C. The
extraction was aided by addition of lime suspension to maintain
alkaline medium. The winning of nicotine from the organic solvent
mixture could well be done by contac with 22% sulfuric acid. The
effects of contact time as well as the organic phase to acid ratio were
studied to determine the optimum sulfation conditions.

Introduction solid and the particle size [ 1]. There are

Leaching is a separation operation four principal types of operating methods
involving washing of a solute adhering to used 111 leaching: the single stage
the surface of a solid. The method is operation, multistage co-current (parallel)
governed by the proportion of soluble system, continuous counter-current
constituent present, its distribution multistage system and multistage counter
throughout the solid, the nature of the
**Department of chemical engineering, University of Technology, Baghdad, Iraq.
* Ibnul-Beetar Research Center, Ministry of Industry and Minerals, Baghdad, Iraq.

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Engineering & Technology, Vol.21, No.8, 2002 Optimization Of The Nicotine Sulfate Preparation
From Tobacco Wastes

current contact between the solids and [8, 9]. It reacts with HCl to produce
solvent [2]. nicotine hydrochloride with H2S04 to
In solvent extraction, it is essential produce nicotine sulfate, which is soluble
that the liquid-mixture feed and solvent in water and alcohol [10].
are at least partially if not completely
immiscible. More complicated processes H
I
use two solvents to separate the N
components of a feed. This is called
double solvent or fractional extraction [3].
The primary objective in extraction is to
0 2
S04

affect a net transfer of solute molecules

from the raffinate phase to extract phase.
The transfer process assumes that two 2C10H14N2+H2S04~ (C10H14N2)2.H2S04
resistances in series impede the movement (2)
of solute from one phase to the other; a Nicotine is used as Insecticide;
third resistance at the interface could also fumigant as 40 % solution of nicotine
be considered [ 4]. sulfate was the commonly used form
Leslie et al. [5] employed counter- although the alkaloid itself is sometimes
current extraction for winning nicotine out sold in the free or uncombined state [ 10-
from tobacco juice. Several organic 12]. It was used in the chewing gum
solvents have been used to extract nicotine industry [ 13, 14]. It was also used as
from aqueous solutions. Claffey et al. [ 6] ingredient m some pharmaceutical
studied the distribution coefficient of formulations (10, 15]. Levorotatory
nicotine between water and kerosene and nicotine is readily volatilized and has been
found that temperature was the· most found to be much more toxic than when
important variable. Millen et al. [7] combined with acids to form nonvolatile
studied the influence of initial nicotine salts.
concentration, temperature and pH on the Three commercial processes for the
distribution coefficients of nicotine recovery of nicotine from tobacco are
between hexane and water. They found used: Steam distillation involves
that the coefficient was temperature and extraction with steam and nicotine is then
pH dependent. removed from the vapour phase either by
Nicotine is a very hygroscopic, direct absorption in sulfuric acid or by
colorless to · pale yellow, unpleasant odor, liquid-liquid extraction after condensation
oily liquid, boiling at 246 'C. Chemically, [16]; Nicotine is extracted from water
it is a diproticbasewithpK(a'(sof3.12 phase by a two-stage liquid-liquid
(pyridine ring) and 8.02 (pyrrolidine ring) extraction process [6]. Nicotine is first

585
Engineering & Technology, Vol.21, No.8, 2002 Optimization Of The Nicotine Sulfate Preparation
From Tobacco Wastes

extracted from water by solvent, and then 8. Glacial acetic acid, (analar), crystal
extracted from the solvent by sulfuric acid violet indicator and methyl red
producing 40 % nicotine sulfate. Kulkarni indicator were from Reidel-de Haen.
[17] recoved nicotine from tobacco waste
stream using sulfuric acid and suitably Apparatus:
prepared micro-emulsion media. The data 1. Rotary evaporator: was a 1-liter
in this field is of commercial nature and capacity supplied by Heidolph
hence they are property of the companies. equipped with vacuum pump from
The aim of the present work is at the Robinir and chiller from MGW Lauda,
establishment of optimum conditions for Germany.
the recovery of nicotine as the sulfate. The 2. Centrifuge was a T5 model from
efficiency of nicotine extraction from Janetzki.
tobacco is measured by analysis of 3. pH meter type (Metrohm 3010) was
nicotine content using non-aqueous calibrated with buffer solutions of pH
titration methods [ 18]. = 9.2 and 7.
4. Reaction flask: Pyrex three-necked,
EXPERIMENTAL 250 ml glass flask to which a dropping
Materials: funnel, a condenser and a thermometer
1. Tobacco dust (State Co. Tobacco, were quick fitted. The reaction flask
Baghdad) was screened (EMBED was used for nicotine sulfate
Equation200 m)and then dried preparation.
overnight at 50-60 °C.
2. Standard tobacco juice was from Extraction of Nicotine from tobacco dust:
Murphy Chem.Co. Ltd. In a round bottom flask distilled
3. Hexane (C6> 92%) was from the water was added to the tobacco dust for
State Gas Co., Baghdad. wetting. After 12 h., ethanol was added to
4. Ethanol (95%) was from the National the mixture and mixed, then left for 12 h.
The soaking liquid was separated by press
.
Co. Food Ind.,Baghdad .
5. Calcium hydroxide, Ca(OH)2, was filtration, where the soaked material was
(G.P.R) from ICI. placed in a cotton cloth between two iron
6. Sodium sulfate anhydrous, chloroform plates (2-cm thick) and forced towards
and sulfuric acid (98%) were from each other. The liquid was collected in a
BDH. glass container. The mother liquor was
7. Perchloric acid, (Analar) was from then concentrated in a rotary evaporator
FlukaAG. under reduced pressure.
The solvent mixture, hexane-
chloroform, was added to the concentrated

586
Engineering & Technology, Vol.21, No.8, 2002 Optimization Of The Nicotine Sulfate Preparation
From Tobacco Wastes

aqueous solution together with dry lime Stirring was then stopped and the phases
suspension to keep the pH value at 12. The were allowed to separate in a separating
mixture was then heated to affect funnel. The upper organic layer consists of
liberation of nicotine to be received by the the solvent and unreacted nicotine. The
solvent. The time of extraction was kept Lower aqueous layer consists of nicotine
constant at 30 min. sulfate solution in water as transparent
The resultant solution was separated liquid. The unreacted nicotine was
into two layers, organic and aqueous layer, estimated in the organic phase by non-
by centrifugation at a speed of 3000 rpm aqueous titration. The overall process for
for 10 minutes. The organic layer was then the extraction and the conversion of
transferred into a volumetric flask and 3 g nicotine into the sulfate form is
of anhydrous sodium sulfate were added summarized in Fig. 1.
for overnight dehydration.
Analysis:
Nicotine Sulfate Preparation: Pipet, 20-ml aliquot of the solvent
A set of experiments was carried to contammg nicotine into 125-ml flask
study the action of two variables on adding 2 drops of 0.02 wt./vol. % of
the percentage conversion of nicotine into crystal violet indicator solution in glacial
nicotine sulfate: acetic acid and titrate to the green end
1- The contact time of the organic phase point with standardized 0.1 N perchloric
with acid solution. acid in glacial acetic acid. All analyses
2- The volume ratio of acid solution to were performed in triplicate. Calculate the
the organic phase. extraction effeiciency (E%):
The concentration of sulfuric acid
solution and the temperature of the system Nie. In sol. wt%= [(Vol. HC104 x O.lN x
were kept constant at 22 vol.% and 30 ± 1 32.45)/100 g] x 100%
\C respectively through out the E% =[(wt%)/ 1.4] x 100%
experiments. Design of the experiments is Where:
shown in Table 1. 1.4 is Nie wt% in tobacco dust (Done
in the Company)
Procedure: 32.45 is the factor of calculation fro
The organic phase containing 1.2 ref.18.
wt.% nicotine was admixed with methyl
red as an indicator. Sulfuric acid solution, RESULTS AND DISCUSSION
22 vol. %, was added gradually from a The water extract of nicotine was
dropping funnel with continuous stirring. obtained in accordance with the detailed
The temperature was maintained at 30 \C. study published else where [19]. The

587
Engineering & Technology, Vol.21, No.8, 2002 Optimization Of The Nicotine Sulfate Preparation
From Tobacco Wastes

extraction of nicotine from the aqueous leads to a gradual increase of (conversion

concentrate was studied in terms of three %), where after the conversion decreases.
variables: organic solvent mixture The effect might be attributed to the
(chloroform/ hexane) to water ratio (SI A), partial oxidation of nicotine by excess
the chloroform content of the organic sulfuric acid at the reaction time. Thus,
solvent mixture and the temperature. The 0.25 volume ratio of acid to organic was
effect of phase ratio (SI A) on the considered here to be the optimum value.
extraction efficiency (E %) is shown in The effect of the percentage
Fig. 2 keeping the other two variables conversion of varying time was studied at
constant at chloroform/ solvent of 7 .5 vol. three different volume ratios of acid to
% and temperature of 40 :C respectively. organic phase. The principal effect is
It is clear that at a ratio of 1: 1 maximum shown graphically in Fig. 6, at time
Eo/o can be obtained. On the other hand the intervals of 5, 10, and 15 minutes
effect of chloroform content in the solvent respectively. The percentage conversion
mixture on E % is shown in Fig. 3 keeping increases rapidly with increasing the time
the other two variables constant at solvent/ to 1 0 minutes then decreases because large
aqueous of 1: 1 by vol. and temperature of time encourages the hydrolysis of the salt
40 :C respectively. Maximum Eo/o is (nicotine sulfate) (8). The time, therefore,
obtainable within chloroform content in must be kept in the range of 9-11 minutes.
the range 6-8% and the highest value was
at 7.5%. Finally the effect of temperature MATERIAL BALANCE
on E % is shown in Fig. 4 keeping the For the production of one kilogram of
other two variables constant at solvent/ nicotine sulfate (0.4 Kg of nicotine) batch,
aqueous of 1:1 by vol. and the following material quantities may be
chloroform/solvent of 7.5 vol. % required:
respectively. The higher the temperature, 33.0 Kg of screened tobacco dust;
the greater will be the E%. However the 50.0 Kg (50 L) of distilled water,
work must be limited because of the 40.0 Kg (50.0 L) of ethanol;
relatively low boiling point of hexane. These give 123 Kg of slurry. The filtration
of the slurry yeilds:
Experimental Results for Nicotine 82 Kg of filtrate ;
Sulfate: After evaporation under vacuum, the
The percentage conversion of following are recovered:
nicotine into nicotine sulfate is plotted 35.68 Kg of ethanol ( 44.6 L);
versus volume ratio of acid solution to 46 Kg of aqueous solution (Tobacco
organic as shown in Fig. 5. Increasing the juice);
acid/organic volumetric ratio to about 0.25

588
Engineering & Technology, Vol.21, No.8, 2002 Optimization Of The Nicotine Sulfate Preparation
From Tobacco Wastes

For solvent extraction, the following are Liquid mixture/tobacco = 3:1 v/w;
added to the aqueous solution: alcohol/water= 1: 1 v/v and
27.6 Kg of hexane ( 41 L) soaking time= 24 hours.
4.96 Kg of chloroform (3.5 L); 2. Liquid-liquid extraction
24.2 Kg of 7 wt% of Ca(OH)2 suspension SIA = 1 :1 v/v; chloroform/ solvent= 7.5
(0.333 Kg of solid Ca(OH)2; % by volume at 40 ~c.
The three variables of the volumetric
After extraction and separation of phases, solvent to aqueous phase ratio (S/ A),
we get: volumetric percentage of chloroform to
32.8 Kg of organic extract; solvent ratio (CHC13/S) and temperature
70.5 Kg of aqueous raffinate; (T) of the system effect on the extraction
A second extraction step requires efficiency in the order:
treatment of the aqueous phase with: (CHC13/S) > (S/A) > T.
41.5 Kg of hexane ( 62 L);
7 .5 Kg of chloroform ( 5 .3 L ); The optimum operating conditions for
36.9 Kg of Ca(OH)2 suspension; the best percentage conversion of nicotine
into nicotine sulfate are: 10 min. react,ism
After phase separation we get: time, the volume ratio of sulfuric acid
49 .1 Kg of organic extract; solution (22 %) to the organic solvent is
107 Kg of raffinate drain; 0.25 by volume. At these conditions the
percentage conversion into nicotine sulfate
The organic extracts of the two steps are is 98 %.
combined for the preparation of nicotine
sulfate by treatment with: REFERENCES
32.2 Kg of 22% sulfuric acid solution. 1- Schweitzer, P. A., "Handbook of
Separation Techniques for Chemical
After complete reaction the separation of Engineering", 3rd Ed., McGraw Hill,
phases gives: N.Y. 1979.
81 Kg of organic layer to be recycled and 2- Cofield, E.P., "Methods of Operating
33.1 Kg of aqueous solution of nicotine Extraction Processes", Vol.58, p. 127,
sulfate. 1951.
3- Treybal, R.E., "Mass transfer
CONCLUSIONS Operation", 3rd Ed., McGraw Hill,
The optimum operating conditions 1981.
for the recovery of nicotine from 4- Jimmy, L.; J.Humphrey, J; Antonio, R.
tobacco wastes are: and Fair, R.,"The Essentials of
1. Soaking Step:

589
Engineering & Technology, Vol.21, No.8, 2002 Optimization Of The Nicotine Sulfate Preparation
From Tobacco Wastes

Extraction", Chemical Engineering, 13- Zander, A. P.; Findlay, T.; B.

Vol. 17,1984. Renner and Sellergren, Anal. Chem.,
5- Leslie D.C.; ,Millen ; Murphy, W.R., 70, 15, (1998).
Ind. Eng. Chem. Res., 32 , No. 12 , 14- Sellergren, B., Zander A. and A.
1993. Sweitlow, J. Chromatog., 829 (1998)
6- Claffey, J.B.; Badgett, C.O.; No. 1-2.
Skalamera, J.J. and Phillip, G.W., Ind. 15- Ray, Q. and E.W. Brewster,"
and Eng. Chem., 42 166 (1950) . Organic Chemistry", Prentice Hall, 3rd
7- Millen, C. and Raymond, W., Ind. and Ed., 1971, p. 751.
Eng. Chemistry Research, Vol. 33, No. 16- Smith, C.R., Ind. Eng. Chem.,
12,pag.3238-40, 1994. 34,251,(1942).
8- Siems, W.F., Hill, H.H. and Hannan, 1 7- Kulkarni B.D, Science of
R.M., Chromatog, J., 811 157(1998). Technology, Sept. 28, (1465-77),
9- Manske, R.H.F., "Chemistry and 1993.
Physiology of Alkalloids" Vol. 1 1959, 18- Faster, D.S. and Leslie, E.S.," The
p.231. Encyclopedia of Industrial Chemical
10- Budavari .S. "The Merck Index", Analysis", Vol. 16, p 134,1974.
Merck and Co.Inc., Rahway, 19- Barbooti, M. M., Zablouk ,M.A.
USA, 11th ed., 1989. and Ramadhan, Sh. T., in press.
11- Deang, E. R., Ind. Eng. Chem.,
vol. 16 ,1275 ,(1924).
12- Asian Pacefic Center for Transfer
of Technology, ID: APC 5044-TO,
From Internet, Sept. 2000.

Table 1: Experimental Work for Conversion

of Nicotine into Nicotine Sulfate.

Exp. Contact Acid I Organic Solution

No Time (min.) (Vol.)
I 5 0.15
2 5 0.25
3 5 0.5
4 10 0.15
5 10 0.25
6 10 0.5
7 15 0.15
8 15 0.25
9 15 0.5

590
 Engineering & Technology, Vol.21, No.8, 2002 Optimization Of The Nicotine Sulfate Preparation
From Tobacco Wastes

D.\,/. Ethanol (95%)

i i
Soaking Tobacco Tobacco Concentration
Toh acco
-... - Filtratiorv .
L

(Evaporator)
Juice
Dus t Soakinq

i
Settler
i
Distilled alcohol
Li.me
Solvent Mb..1:.

~r , P'
Aqueous
Sulfation Extract Solution
-~ Separation
~- Extraction ~
~
!
'

+
NICOTINE ,.
SULFATE Raffinate

Figure 1: Block diagram of ex,perimental work

100,
• (CHLOf/S)
I
I =7.So/o,
80 •
'IEMP.=40C
60
~
r.il
40

20

0
0.6 0.7 0.8 0.9 I I.I 1.2 1.3
(SIA)\a...

Figure 2: Extraction Efficiency of Nicotine vs. phase ratio at optimum

values of (temperature and chloroform content in the solvent mixture)

591
Engineering & Technology, Vol.21, No.8, 2002 Optimization Of The Nicotine Sulfate Preparation
From Tobacco Wastes

~ (S/A)VOL=
100 1 :l(vol.),
90
80
Temp.=40c'
70
60
.50
~
0 40
~ 30
20
10
0 I t I I f I I I '•'I

I
L __
0 2 ~ t.
(CHLOR ./S)(VOL.) ~;,
8 JO

_J
figure 3: Extraction Efficiency of Nicotine , . s. chloroform content in the
solvent mixture at optimum values of (temperature and phase ratio)
J

. I
I
I
I

90 • (S/A)(VOL.)-.!l: 1
(CHLORJS)VOL.%
-"7.5%
88

86
~
Q )

~
84

82

80
0 5 10 15 20 25 30 35 40
Temp.(c')

Figure 4: Extraction Efficiency of Nicotine vs. temperature at optimum

values of (phase ratio & chloroform content in the solvent)

592
Engineering & Technology, Vol.21, No.8, 2002 Optimization Of The Nicotine Sulfate Preparation
From Tobacco Wastes

100

Time(min)
90

--.-5 -6-lQ
80 -1.-15
c:
0
·;;;
...
c:;
;;... 70
c:
0
II ....
l 60
I
I

50
0 0.1 0.2 0.3 0.4 0.5 0.6
(Acid/Org.)(\'ol)

Figure 5: Conversion % vs. volumetric acid to organic phase ratio

at different reaction time.

100 (Acid/organic )vol.

90
-+-.125
cQ
·-t:~
80
70
--.25
:--*-.5
>c
Q
(.I
60

50
0 5 10 15 2D
Time(min)

Figure 6: Conversion % vs. reaction time at various acid to organic

phase ratio.

593