Journal of Scientific & I ndustria l Research

Vol . 60. September 200 1 . pp 738-747

Identification and Utilization of Banana Plant Juice and Its Pulping

Liquor as Anti-Corrosive Materials

Mohamed EI-Sayed ' . O l fa! Y Mansour'. I brahim Z Sel im' and Maha M Ibrahim"

'Chemi stry Department. Faculty of Science. Alexandria University. A lexandria. Egypt 2Cel lu lose and Paper Department and 'Physical Chemistry Department. N ational Research Center. Dok k i . Cairo. Egypt

Received: 1 0 J anuary 200 1 ; accepted: 1 4 May 200 1

B anana pl ant juice. taken from paradica and maghraby banana pseudostem. as well as black l iquor result ing from pulping the banana plant with ei ther 10 or 23 per cent sodium hydroxide ( w/wl, were ident ified for their chemical composition. On the

other hand the use of these admixtures as anti -corrosive materials was studied by applying the weight loss method. The resul ts indicate that the maximum inhibition varies according to the ant i-corrosive material used. The addit ion of the banana plant j uice

leads to an i ncrease in the protection per cent. s ince i t forms a protected layer on the concrete steel surface and hence prevent it from corrosion.

Introduction Banana p lant juice is a transparent solution which runs

out from the pseudostem when the banana p lant is cuI and it represents 90 per cent of the pseudostem weight . This ju ice becomes p ink when exposed to air and after some time changes to l ight brown .

After harvesting the banana wastes were used to pro­duce pulp and paper us ing e ither 1 0 or 23 per cent ( w/w) sodium hydroxide as pu lping reagent . The resu lt ing black l iquor from the pulping process caused env ironmental pol lut ion .

Corrosion is a problem caused by nature; it affects material substance and is governed by energy changes . There are many corrosion reactions i n what can be con­sidered as dry environment . Furthermore. corrosion can occur in the atmosphere where the presence of water vapour, together with an ionic material from any avialable source. is enouh to cause corros ion for the same reasons as if the metal were i mmersed I .

I n the present study, a natural admixture from banana plant j u ice taken from paradica and maghraby banana pseudostem, as well as the resul t ing black l iquor. has been identified for their chemical composit ion and ut i­l ized as concrete adm ixture. The admixture effect cor­rosion res istance against surrounding aggress ive media has been i nvestigated, apply ing the weight loss method .

* Author for correspondence

Experimental

Chemical Analysis otThe Investiated Banana Plant Juice

and The Black Liquor

The banana plant ju ice and the a lkal ine pulp ing black l iquor were studied for their chemical analys i s and com­posit ion. pH, sol id content and density were stud ied for the banana p lant ju ice, as wel l as the res idual alkal in i ty and l ign in content for the a lkal ine pulping black l iquor2 .

On the other hand, identification to the chemical com­posit ion of the alkal ine black l iquor resu l t ing by the use of 1 0 and 23 per cent sodium hydroxide for pU lpi ng. as wel l as the banana plant j u ice. was stud ied . D isti l lation was carried out and the residual sol id left was then dried in an oven at 1 05° C. The n itration test was carried out for the sol id residue. Gas chromatography-mass spec­trometry (GC-MS) was carried out in order to know the compounds present in both the black l iquor and the ba­nana p lant juice using DB-5 column between 50-300sym­bol 1 76 \f "Symbol"C for 40 m in .

BOllana Piant Juice {lnd Black Liquor {lS Anti-corrosil 'l'

Materials

The admixtur� of the banana plant ju ice, as wel l as black l iquor, resul t ing from pUlping the banana with e i ­ther 1 0 or 23 per cent sodium hydroxide (w/w ) , were lIsed as anti-corrosive materials by apply ing the weight loss method. In this method, a concrete steel sample of known composit ion (98 .586 per cent Fe, 0 .3 per cent C,

� I

I "

EL-SAYED e/ al. : BANANA PLANT J UICE & ITS PULPING LIQUOR 739

1 2

1 0

8

RIC

2 2 2 9

2 8 1 1 2 8 : 3 0

1 . 5 4 E + 0 9

6 8 9 5 1 5 6 0 2 3 : 0 5 1 1 : 0 7 1 7 : 0 5 4 8 2 6 1 3 8 0

3 0 2 2 4 06 8 3 3 9 3 2 3 3 2

4 2 3 5 6 6 6 1 3 9 4 1 9 9 4 2 6 7 3 5 : 1 2 9 : 0 3 1 5 : 3 5 2 0 : 5 9 2 7 : i 1

3 4 0 0 6 2 1 2 7 6 6 8 5 5 3 0 2 6 7 6 8 4 5 2 8 4 8 4 4 9 /. 3 9 :

2

0 ���������������41�L�������mwl 1 0 0 0 2 0 0 0 3 0 00

Figure I -Gas chromatographic analysis of banana plant j uicc

0.045 per cnt S , 0 .72 per cent Mn, 0.033 pr cent P, 0 .2 per cent S i , 0.044 per cent Ni , 0 .054 per cent Cr, 0 .0 1 3 per cent Mo, and 0.0 1 5 per cent V), known weight, and measured area, after pol ishing and clean i ng, were placed in a 250 mL beaker contain ing 50 mL sodium chloride solution, as corrosive media, w i th 1 0, 30, and 50 mL of the different admixtures u sed, and left for 7 d. The samples were then removed from the solution, washed w i t h d i s t i l l ed water, dr ied w i t h acetone and then rewighed. The weight loss was determined and the rate of corrosion was calculated as g/t/cm2 according to the fol lowing equation :

Rate of corrosion (r) = (Weight loss / t ime) / area.

Also the per cent of protection is calculated as fol lows :

Per cent protection = ------ X 1 00, r

"

where r" i s the rate of corrosion in the absence of i nhibi­tor, and r i s the rate of corrosion in presence of inhib i tor.

Results and Discussion Chemical Analvsis ol The Banana Plan! Juice

Laboratory measurements for the banana p lant ju ice indicated that its pH ranged from 4.73 to 6.0, den;i ty =

1 .024 g/cm3 and its sol id content i s 7 . 89 per cent . The chemical composition of the banana plant juice was iden­t ified by n i tration test, as wel l as GC-MS techn ique. S i ngh and Atk inson3 found that the separation and de­tection of the banana plant ju ice indicates the presence of two major acti ve components, potass ium ni trate and magnesium n itrate. The n itration test, appl ied for the sol id residue, indicates that the ju ice i s an aromatic compound, whi le the GC-MS techn ique exhibited several peaks with different retention t imes, as shown i n Figure I . The e lec­tron impact-mass spectra (EI-M S ) of each indi vidual chromatographic peak i ndicates the molecu lar weights having fol lowing structures (Figures 2-5) :

740

1 0 0

a D

6 Q

4 0

2 0

1 0 0

a O

6 0

4 0

96 . 3 J

2 0 6 . 9

1 1 1 5 . ) �JiJd� . J • 2 0 0

J SCI IND RES VOL 60 SEPTEMBER 200 1

I 4 0 0 I 6 0 0 I 800

Figure 2-Mass spectrum analysis of banana plant juice with retention time of 4: 40 min

1 7 6 . 9

1 ) 3 0

2 0 1 1 9..2

I 200 ado

Figure 3-Mass spectrum analysis of banana plant juice with retention time of 7:55 min

I 1 0 00

E+ 05 2 . 9 6

E+ O S 6 . 2 4

I '

I

�

(a)

I ,

EL-SA YEO et al.: BANANA PLANT JUICE & ITS PULPING LIQUOR 74 1

100

80

60

4 0

20

133 . 1

o

E. os 1 . 4 6

Figure 4--Mass spectrum analysis of banana plant juice with retention time of 1 2: 42 min

2 5 6 . 1 1 0 0

8 0

6 0

7 3 . 3 4 0 1 2 9 . 1

2 1 3 . 1 2 0

IJl l1 IHJ 200 400 600 800 1000

Figure 5-Mass spectrum analysis of banana plant juice with retention time of 23 : 05 min

For retention time 4:40 min, it has molecular weight of 206.9 (Figure 2), which has the molecu­lar formula C14H220, i .e . • Octyloxybenzene :

�O'f(VVV m/e 206

/ \ � o o m / e 93 m / e 113

(b) For retention time 7 :55 min, it has molecular weight of 1 76.9 (Figure 3), which has the molecu­lar formula C I()H I 2N20, Serotonine or 3 -( 2-

aminoethyl)- 1 H-indol-5-ol, having the following structure :

H H �N� --. (PN� HO�CH2CH2 NH 2 H�

m / e 1769 m I e 133 Serotonin

m / e 116

742 J SCI IND RES VOL 60 SEPTEMBER 2001

(c) For retention time 1 2:42 min, it has molecular weight of 354.9 (Figure 4), which has the ·molecu­lar formula of C20HI sClN202. 1 -[5-(2-amino-4'­chloro- l , I ' -oxybisbenzene )]-5-hydroxyindol, hav­ing the following structure:

� HO -� HO m / e 356 m I e 223

1

� HO 9 +-- � m / e 133 HO

m I e 207

(d) For retention time 23:05 min, it has molecular weight of256. 1 (Figure 5), which has the molecu­lar formula C17H2 1N2' 4,4 '-methylenebis(N,N­dimethylbenzeneamine), having the following structure :

�I '/"" I ,, � � / N N / '\

m I e 254.38 m I e 210

m Ie 77

Chemical Analysis of Alkaline Pulping Black Liquor In alkaline pulping the spent cooking liquor from the

digester plus the filtrate from the washing separation is commonly known as black liquor. It contains, practically, all the alkali originally added, together with over half the original weight of the raw material4.

Table 1 shows the analysis of the black liquor due to cooking the banana plant with 10 and 23 per cent so­dium hydroxide (w/w). The pH ranged between 1 1 .4 to 1 2.3, owing to the presence of residual alkali. The den­sity ranged from 1 .038 to 1 .06 1 g/cm3. The solid con-

tent, which is measured as gil 00 mL black liquor, is high for the black liquor, resulting from cooking with 23 per cent sodium hydroxide (w/w) than that of 1 0 per cent sodium hydroxide (w/w), and this is due to the presence of more lignin and inorganic residual . The high lignin obtained as shown in Table 1 , cleared that, delignification rate is high with 23 per cent sodium hydroxide (w/w) than with 10 per cent sodium hydroxide (w/w) using the same pulping conditions .

On the other hand, analysis of the chemical composi­tion present in the alkaline black liquor resulting from using 10 and 23 per cent sodium hydroxide for pulping was studied using GC-MS technique. The chromato­grams exhibited several peaks which are identical with their retention times, as shown in Figure 6 and 7. The electron impact-mass spectra (EI-MS) of each individual chromatographic peak indicate the molecular weights of the different peaks, having the following structures :

HO

�o � I

HO

� HO m ' e 355

g ---

m HO m I e 207

L � HO

m I e 1 33

m I e 240

o H� �

m I e 224

(a) For retention time 5 : 1 9 min, it has molecular weight 355.6 (Figure 8), which has the molecular formula of C22H27N03' 1 -[6-( I -hydroxy-4-octyloxy-ben-

J '

�

t \

EL-SAYED et aL.: BANANA PLANT JUICE & ITS PULPING LIQUOR

Table I - Analysis of the black liquor from different alkaline pulping processes

Per cent NaOH pH Density Solid content Residual Residual Lignin used for pulping

10 per cent 23 per cent

RIC

1 2

1 0

1 1 .4 1 2.3

5 7 1 8 : 1 3

1 8 0 e 1 9 9

glcm) gl l OO mL

1 .038 1 .06 1

1 2 0 5 1 3 : 5 4

3 8 1 2 9 9 7

liquor

7.93 1 6.76

2 0 7 9 2 1 : 5 6 5 6 5 4 4 5 80

1 7 0 5 1 8 : 2 4 .

9 2 68 5 2 8

2744

2 8 : 3 1 1 . 7 9 r. + 0 9

alkalinity alkalinity gIL(as NaOH) gl8L (as NaOH)

1 8.46 22.46

1 47.6 1 79.6

3 8 0 2 3 9 : 1 3

300654 1 2

gil

2 1 .05 29.87

Figure 6--Gas chromatographic analysis of black liquor resulting from pulping banana plant with 10 per cent NaOH

RIC

50

40

�o

2 0

1 0

a

1 1 ) 6 1 3 : 1 5

4 4 8 4 5 9 9

n o ) 1 2 : 5 7

1 2 3 5 4 7 0

1 000

2 1 97 2 2 : 4 6

2 1 4 7 7 2 8 2

1 9 4 5 2 0 : 3 0

4 3 H 3 4 1

2 0 0 0

2 8 1 2 2 8 : 2 8

4 3 3 9 6 4 9 2

2 7 0 0 2 7 : 2 4

7 4 7 1 6 0

2 6 4 0 2 6,: 5 0

7 5 8 5 9

3 0 0 0

) 3 1 1 ) ) : 2 3

2" 2 8 1 6 5 3

E + 0 6 4 . 3 7 8

4 0 0 0

Figure 7-Gas chromatographic analysis of black liquor resulting from pulping banana plant with 23 per cent NaOH

743

744 J SCI IND RES VOL 60 SEPTEMBER 2001

1 0 0

8 0

60

40

20

2 0 6 . 9

1 3 3 . 0 2 2 4 . a

1. 1 .J ., .1 t J [ill . a "

ado I 1 0 00

E+ 0 5 2 . 6 6

Figure 8 -Mass spectrum analysis of black liquor results at retention time of 5: 1 9 min '

zene)]-5-hydroxyindol, having the following struc­ture :

HO

(ik HO � � HO

m / e 355

-� HO

m I e 207

L � HO m I e 133

m I e 240

en H� �

m I e 224

(b) For retention time 8: 1 3 min, it has molecular weight 207 . 1 (Fi gure 9), has the molecu lar formula

CI IH ,3N03, 3,5-dihydroxy- l -ethyl-4-methoxyindol, having the following structure :

C�CH 3 \V

- m HO � OH m / e 176.9

HO � m / e 133

m / e 150.9

(c) For retention time 1 2:05 min, it has molecular weight 206.6 (Figure 1 0), having the molecular formula of C '2H I7N02' 1 -( 4-amino-3-ethyl-5-methoxypheny 1)­I -propanone, having the following structure :

Admixture Effect on the Corrosion Behaviour Concrete is essentially an alkaline medium (pH 1 2.5)

in which the reinforced steel is protected against corro­sion by the formation of a passive layer of iron oxide. However, since concrete is a porous material, moisture,

I '

1 00

80

60

40

20

1 0 0

8 0

6 0

1 0 4 0

\ 2 0

EL·SAYED et al.: BANANA PLANT JUICE & ITS PULPING LIQUOR

1 ) 3 . 1

1 0 . 9

��'��' ���[��Lr��+:'�i'�'� .. ri �i'�I�'�lrI TI�I'��ii�i���I�li�11�lf�I�'�II�i��i'Ti�"�'�I�i �l'��,,�,,�,�il �

E+ 0 5 1 . 7 9

2 0 0 4 0 0 6 0·0 8 0 0 1 0 00

Figure 9-Mass spectrum analysis of black liquor results at retention time of 8: 13 min

1 3 3 . 0

. 5

2 0 0 4 0 0 6 0 800

Figure 1 00Mass spectrum analysis of black liquor results at retention time of 1 2: 05 min

1 00 0

E+ 0 5 1 . 8 6

745

746 J SCI IND RES VOL 60 SEPTEMBER 200 I

o II ))"CH2 CH 3 _

H3 C� CH 2 CH 3 NH 2 m / e 206

o II C

6 m/e 105

... -/.-m / e 177 m / e 149

m / e 133

Table 2 - Effect of sodium chloride (0.5M) as corrosive material on concrete steel

Duration. d Weight loss. g Rate of corrosion

0.0062 3 . 1 2 X 1 04 2 0.0072 1 .9 1 2 x 1 04 3 0.0086 1 .443 x 1 04 4 0.0 1 08 1 .358 x 1 04 5 0.0 1 44 1 .449 x 1 04 6 0.02 1 6 1 .8 1 2 x 1 04 7 0.0432 3. 1 05 x 1 04

oxygen and salt are free to penetrate and disrupt the pas­sive iron oxide filmS. Chloride ions have been found to break down this film, and still remain in solution, thereby allowing them free to break down additional protective layers6.7

The weight loss behaviour of concrete steel immersed in a solution ofO.5M sodium chloride, as aggressive ions is shown in Table 2 .

I t can be noticed that the weight loss increases with time. The effect of admixture upon suppression of the corrosion of reinforced steel during its service in aggres­sive environment has also been evaluated. The concrete steel was immersed in a solution of 0.5M NaCI (as con­trol sample in this case), admixed with 20, 60 and 1 00 per cent banana plant juice, as well as alkaline black liquor, as inhibitor admixtures by applying the weight loss method. The relation between the time and weight loss, and the per cent of addition and per cent of protec­tion are shown in Figure 1 1 and ] 2. It can be noticed that banana plant juice can be used as an anti-corrosive ma­terial without l imitations, since increase in the percent-

0.05 "T-=i20h. ... ;-;; .. ;;..,-;; ... ;;;.,LI./_=-+. ;0;",,-;; .. ;-;, .. ;;: .. ;-;:p;::b .. :;-;j=_:-illF.'";;;J .... �. :-c .... ::-... ,-;--:-.. .,-i_-, .lOper eMl ••• et J�.1 *Io,.r <:It.' blac. .. �I -+ 'OOper ClAt .1 ... li.il .z:o,., ... w.ct 1 ... 11 -I.Hpc • .. "l w.a .... . 1 ..... tw .. .. U litll .- 0.'" HaCJ 0.04

0,0.03 � Q t J � O.02

0.01

2 3 4 5

• ,

7 8 Time, d

Figure I I-The relation between weight loss and time

1 00

80

� 60 to) .! e Q. -c: II) to) 40 "-II) a.

20

</<1-i'�

,F� ---------.. (J-'> �o..<3o\

*' , .:

�40" � / "0, .

�,/

�. q,�

��. �-,,"<: � �'"

o 1 0 20 30 40 50 60 70 80 90 1 00 1 1 0 Per cent addition

Figure 1 2-The relation between per cent of protection and addition

I \

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EL-SAYED et al.: BANANA PLANT JUICE & ITS PULPING LIQUOR 747

age of addition, results in an increase in the protection percentage. In the case of the black liquor results from pulping the banana plant with 23 per cent NaOH (w/w) (black liquor II), it can be used as an anti-corrosive ma­terial till 60 per cent of addition, since increase in the percentage of addition after this, results in a decrease in the protection percentage, while for that produced by pulping with 1 0 per cent NaOH (w/w) (black liquor I), i t can be used as an anti-corrosive material til l 20 per cent of addition only.

As mentioned earlier that both banana plant juice and black liquor comprise compounds with aromatic ring, so they form a layer on the steel surface by adsorption process through the 1t-bond of the aromatic ring and hence prevents the metal from corrosion. On the other hand the presence of the nitrogen atom in some com­pounds can also form a layer by the adsorption on the metal surface through the lone pair of electrons forming a chelating bond, for preventing the metal from corro­sion.

From the earlier results, one can conclude that, steel reinforcement could effectively sustain the deleterious effects of aggressive ions in the environment surround­ing the concrete when the latter has been mixed with either banana plant juice or its black liquor as anti-cor­rosive materials.

References I Trethewey K R & Chamberlain J, Corrosion, for studellls of

science and engineering (John Wiley & Sons, lne., New York), 1 988, pp 1 7-37.

2 Mansour 0 Y, Nagaty A & EI-Khatib M M, Indian J Clwm Technol, 5 ( 1 998), 7- 1 5.

3 Singh R P & Atkinson E S, The bleaching of pulp, edited by Singh R P (Tappi Press, Atlanta) 1 979 pp 80- 1 00.

4 Casey J P, Pulp and paper; chemistry and chemical tecllllol­

ogy, Vol. I, Sec ed (Interseienee Publisher, Inc., New York) 1 960.

. 5 Tantawi S H & Selim I Z, J Mater Sci Teehnol, 12 ( 1 996) 95-99.

6 EI-Sayed H A, Cementa, 4 ( 1 992) 209.

7 Verbeek G H, Corras Sci, 34 ( 1 986) I I .