Extraction of Castor Oil from Castor Seeds Noman m.

Haimour and Ammar Al-Omari Amman Jordan ABSTRACT

Physical and chemical characteristics of Jordanian Castor Seed and Castor Oil are similar to that produced in the other countries. Oil Content of Jordanian Castor Seed was determined to be ( 50. ! ). Leaching of castor oil was done using hexane and erosene sol!ents. "he leaching process is influenced by many factors. "he following factors were studied in this wor # sol!ent$solid ratio# mixing speed# temperature# and sol!ent type. "he rate of leaching was !ery high initially for time less thane %& minutes followed by slow leaching stages. "he mathematical models of Patricelli et al. ( '()( ) *'+# and So( '(,- ) *%+ were applied to the experimental data. .ood agreement between the experimental and theoretical data was obtained. /inetic coefficients for the washing and diffusion stages for both models were determined. Introduction Castor oil is a !egetable oil . 0t is obtained from the seed of the plant 1icinus communis # which grows wild in the most tropical and subtropical areas# but it is grown as an annual crop in 2ra3il # and 0ndia . "he a!erage oil

content of the seed is 45 percent # but may !ary from 65 to 55 percent (2ernardini # '(,5 ) *6+. 2ra3il is the largest producer of castor seed in the world . "ogether with 0ndia they produce about 55 7 -&8 of castor seed produced in the world (S2P)*4+. Castor oil tree plants are mainly grown for its seed # the oil from which is used as a lubricant and in other applications . "he ca e is mainly used as manure . 1ecent research ( S2P )*4+ has shown that the stems could also be used in the paper industry . "he common methods of oil expression or leaching are applicable to castor oil # with certain limitations owing to the nature of the material . Since the seed contains toxic materials # castor oils are not usually processed in e9uipment in which other oil seeds are to be wor ed . Literature Survey 2oucher et al ( '(4% ) *5+ wor ed on porous clay plates impregnated with phosphatide:free soybean oil and with tetrachloroethylene as a sol!ent . ;e found that li9uid film resistance to the transfer of oil to the sol!ent was inconse9uential as compared to the resistance to diffusion within the plates and the diffusion coefficient was found to be simply a function of the !iscosities of sol!ent and oil.

<an et al ( '(4, ) carried out a mathematical analysis indicated that rapidly extractable oil was caused by the opening of a certain number of oil: bearing cells in slicing the oil seeds# plus the occurrence of !oid spaces in the seeds after drying. Osburn and /at3 ( '(44 ) indicated that the ma=or obstacle to extraction is probably diffusion through the cell walls and that the initial rapid extraction is to be attributed to cell destruction. "he proportion of easily extractable oil was found to decrease with slice thic ness. 0t may be noted that with simple diffusion an increase in the extraction temperature can be expected to increase the extraction rate by lowering the !iscosities of sol!ent and oil . /arnofs y ( '(4, ) obser!ed that in one case increasing the temperature from '&& < to '(% < the time re9uired to lower the oil content of cottonseed fla es to 68 with heptane reduced by ,&8 . >ingard and Phillips ( '(5& ) found that the time re9uired to reduce oil seeds to '8 residual oil content !aries with a power of the temperature that # with cottonseed# soybean # and flaxseed fla es and hexane as a sol!ent # ranges from 7'.( to 7%.4 . Othmer and ?garwal ( '(55 )*-+# found that the rate of extraction of soybean is proportional to the 6.5 power of the oil remaining in the fla es at

any time of the extraction# and the rate decreases approximately as the fla e thic ness raised to the fourth power. Coats and >ingard ( '(5& )*)+ found that hexane extraction of soybean# cottonseed# flaxseed# and peanuts# as either fla es or crac ed particles ( grits )# conformed to the mathematical formula T=KDn , where T is the time re9uired to reduce the material to a residual oil content of '.&8 ( on a dry sol!ent free basis )# D is the fla e thic ness or grit diameter# K and n are constants. ?pproximate !alues found for n were# for soybean fla es range from %.6 to %.5@ for cottonseed fla es# '.5@ for flaxseed# )# and for peanut fla es# 6.%. Patricelli et al ( '()( ) *'+ studied the extraction of sunflower seeds and proposed a two stage mathematical model based on two mechanisms# washing and diffusion. 0n the washing stage a ma=or part of the oil is remo!ed by simple washing which corresponds to a high rate of transfer of oil from the solid surface to the sol!ent during the initial period of the extraction process# while in the diffusion stage the remaining oil is extracted through a diffusional process ha!ing a low rate of transfer of oil from within the solid to the sol!ent and become significant after the washing stage is complete. "he final expression of the mathematical model is presented by e9uation ( ' ) #

w C L = C L ' exp

w c .t

) } + C { ' exp(
d L

d c .t

) } ..( ' )

So and Aacdonald ( '(,- )*%+ studied the applicability of the mathematical model of Patricelli et al on the extraction of canola oil. ? modified !ersion of the abo!e mathematical model was studied by So# in which he considered two types of diffusional processes occurring within the seed B unhindered diffusion of oil held in the ruptured cells of the seeds @ and hindered diffusion of oil from unruptured cells . "his modified model is represented by e9uation ( % )

w C = C L ' exp L

d% C L

{ ' exp(

w c .t

)}

d' C ' exp L

d% c .t

)}

d' c .t

)}
..............( % )

;aimour and ?bu:<ara ( '((5 )*,+ studied the effect of mixing speed # extraction temperature # sol!ent:solid ratio and the type of the sol!ent used on the extraction of oli!e oil from oli!es expression residues and they found that the mathematical model of Patricelli et al ( '()( )*'+ could be applied to the experimental data # with a good agreement between the experimental and the theoretical results.

E"#ER$%ENTA& A##ARAT'S BATCH E"TRACTOR 2atch leaching was used to study the transient beha!ior of the seed: sol!ent system under !arious experimental conditions. "he batch extractor consists of a two liter glass cylindrical container co!ered with a Plexiglas co!er pro!ided with two holes@ one of them to insert the stirrer shaft# the other to pour the sol!ent and as a sampling hole. Aixing was attained by using a three bladed stainless steel paddle connected to a !ariable speed motor. <our Plexiglas baffles were e!enly spaced around the circumference at (& tra!els to ensure efficient mixing and uniformity of the !essel contents. "he baffles were fixed in the extractor co!er such that# when being in place# they ha!e a clearance with the wall and the bottom of the !essel. "his arrangement assures e!en and smooth mixing without stagnant areas. <igure ( ' ) shows a schematic drawing of the e9uipment illustrating all dimensions.

PROCEDURE

DETERMINATION OF OIL CONTENT OF JORDANIAN CASTOR SEED

1epresentati!e samples of castor seeds were prepared according to the $'#AC STANDARD METHODS [ 9 ] , in which the seeds were rasped by the means of hand rasping to achie!e grains of rasped seeds which might be longer than % mm # but must not exceed 5 mm . <rom these pre!iously prepared samples # representati!e samples were analy3ed for their oil content according to the $'#AC STANDARD METHODS [9]using soxhelt extractor

Extraction Experi ent "he seeds before leaching were crushed and rolled by using meat grinder. "he batch extraction !essel was initially charged with a measured amount of castor seeds and placed in the water bath at the desired temperature. "he sol!ent of about '%&& ml at certain temperature was added on the castor meal in the !essel while the stirrer was rotating at the desired speed . "iming was started when half the sol!ent had been transferred . "his procedure was

used by So *%+ . Samples of the miscella ( sol!ent : oil mixture ) were ta en from the extractor as soon as possible and in an increasing time inter!als for the rest samples until it was felt that little change was occurring in the oil concentration in the sol!ent . Samples were ta en from sampling hole on the !essel co!er by using '& ml pipette # the !olume of each sample was '& ml . Cach sample was transferred to a pre!iously weighed sample bottle . "he miscella samples were analy3ed for oil content by distillation of the ma=or part of sol!ent and eliminating the last traces by drying the sample bottle in the o!en at a specific temperature depending on the boiling point of the sol!ent . "he main !ariables studied in sol!ent leaching were B ': Aixing speed ( rpm ) # %: "emperature ( C ) # 6: Sol!ent $ Solid ratio ( ml $ g )# 4: "he sol!ent used .

RESULTS and DISCUSSION

"he oil content of the seed is 5'8 and the moisture content is 5.68 . "he oil content of the seed ernel is -6.68 while the oil content of seed hull is '.'8 . Oil leached from seed ernel is clear and almost colorless while oil leached from seed hull is dar brown. "he effect of !arious factors on the

leached oil are shown in <igures (% : () . "he results show that leaching rate is !ery high at the beginning then decreases with time . "he cur!es representing the concentration of leached oil as a function of time could be di!ided into two main regions @ in the first one # the rate of leaching is !ery high compared with the second region which indicates that small resistance to leaching exists initially . "his region refers to D>ashing StageE @ where a ma=or part of the oil is remo!ed by simple washing which corresponds to a high inetic coefficients from the solid surface to the sol!ent during the initial period of the leaching process . "he second region has a slow rate of leaching which indicates that high resistance to leaching exists . "his region refers to a DFiffusion StageE @ where the remaining oil is leached through a diffusional process ha!ing a low inetic coefficients from within the solid to the sol!ent and becomes significant after the washing stage is complete . "he mass transfer coefficients for the cases studied are found numerically by using the standard routine program and tabulated in "able ('#%) . "he model proposed by Patricelli et al .*'+ ( model ' ) and the modified model proposed by So *%+ ( model % ) are used to find the mass transfer coefficients ."he different factors # which were studied @ that affect the rate of leaching are B

1- Mixing speed <igure ('&) shows the effect of mixing speed on the concentration of leached oil by using commercial hexane . 0t is shown that the ma=or part of oil is leached within the first %& minutes from the beginning of the leaching process # where the rate of leaching is initially high then it decreases with time . "he results show that as the mixing speed increases # the rate of leaching and the concentration of leached oil increase . "his result indicates that the rate of leaching is significant at the beginning and controlled by an external boundary layer resistance which decreases by increasing the turbulence of the mixture by increasing the mixing speed 0n the second stage # the leaching rate is not affected by mixing speed @ since leaching is controlled by internal resistance # which is not affected by increasing turbulence . "he !alues of mass transfer coefficients are shown in "ables ('#%) . 0t is clear that the !alues of mass transfer coefficients for the washing stage (external mass transfer) are !ery large compared to the coefficients for the diffusion stage ( internal mass transfer ) in the two models . 0n the case of the modified model @ the !alues of mass transfer coefficients in the first diffusion process ( unhindered diffusi n ) are !ery large compared to the coefficients for

the second diffusion stage ( hindered diffusi n ) . 0n all cases the !alues of mass transfer coefficients increase with increasing mixing speed

2- Solvent - Solid ratio <igure ('') shows the effect of the sol!ent:solid ratio on the ! n!entrati n f lea!hed il and the rate f lea!hin" # $t is !lear that the ! n!entrati n f lea!hed il de!reases %& in!reasin" s l'ent(s lid rati , %ut it is im) rtant t n te that the am unt f lea!hed il in!reases %& in!reasin" the s l'ent(s lid rati sin!e in!reasin" the s l'ent(s lid rati de!reases the il ! n!entrati n in the %ul* +hi!h !ause an in!rease in the dri'in" f r!e f r lea!hin" # The 'alues f mass transfer ! effi!ients in!rease %& in!reasin" s l'ent(s lid rati as sh +n in Ta%le ,-,./ #

3- Extraction temperature <igure ('%) shows the effect of leaching temperature on the concentration of leached oil and the leaching rate . 0t is clear that increasing the leaching temperature increases both the concentration of leached oil and the rate of leaching . ?n increase of about '& C in the leaching temperature increases the percentage of leached oil more than %& 8 . 0t is expected that increasing temperature simplifies both

washing of oil by sol!ent and leaching of oil by diffusional process . Since !iscosities of both oil and sol!ent decrease by increasing temperature and hence flowing of both fluids become more easy. "he !alues of mass transfer coefficients increase by increasing temperature as shown in "able ('#% ) .

4- Type of solvent Commercial hexane was used as the main sol!ent to study factors affecting the concentration of leached oil and the rate of leaching because it has a low boiling point -(.& C ( 2ernardini # '(,5 )*6+ which ma es distillation of hexane easy under atmospheric pressure . <igure ('6) show a comparison between the two sol!ents hexane and erosene on the concentration of leached oil and on the rate of leaching . 0t is clear from <igure ('6) that the concentration of leached oil in the case of erosene as a sol!ent is greater than it for hexane as a sol!ent at the same conditions of temperature # mixing speed # and sol!ent:solid ratio # but the main disad!antage of erosene as a sol!ent is its high initial boiling point which is about '(6 C . "he cost of remo!ing erosene from the leached oil by distillation is greater than it for hexane as a sol!ent since erosene needs more heating to e!aporate or !acuum should be created in the distillation system

which is also cost money . "he !alues of mass transfer coefficients of erosene are higher than them for hexane as shown in "able ('#%) .

CONC&'S$ONS ( Oil content of Jordanian Castor Seed is determined experimentally. Sol!ent leaching of castor oil is influenced by many factors such as sol!ent: solid ratio # mixing speed # temperature and sol!ent types . "hese factors were studied and it is concluded that B : 0n all cases of sol!ent leaching process# more than (&8 of leached oil is reco!ered in the first %& minutes which can be considered the effecti!e time for leaching process. : "he percentage of leached oil increased by increasing the sol!ent:solid ratio# since the dri!ing force increase. : "he rate of leaching increased by increasing the mixing speed. ?fter '% minutes from the beginning of leaching process the oil concentration was 4.&,6 ( g oil$'&&g sol!ent ) at mixing speed G '-& rpm# while the concentration was 5.&( ( g oil$'&&g sol!ent ) at mixing speed G 6-& rpm. : "he rate of leaching increased by increasing the leaching temperature. Hiscosities of both castor oil and the sol!ent decrease by increasing the temperature and hence flowing of both fluids become more easy. ?n increase

of about '& C in the leaching temperature increases the percentage of leached oil more than %&8. : "he rate of leaching and the amount of leached oil increase when using erosene as a sol!ent instead of normal hexane. "he e9uilibrium concentration was ,.(& ( g oil$'&&g sol!ent ) in the case of erosene as a sol!ent# while the e9uilibrium concentration was -.54 ( g oil$'&&g sol!ent ) in the case of hexane. 0t should be noticed that remo!ing the sol!ent in the case of erosene will need more energy than hexane since the boiling point of erosene is much higher than it for hexane. "he mathematical model of Patricelli ( '()( )*'+ and the modified mathematical model of So ( '(,- )*%+ were applied to the experimental data of sol!ent leaching process. .ood agreement between the experimental and theoretical data. "he modified model appears slightly better than the first one but# it is more complex since it considers two diffusion stages while the first model considers only one diffusion stage. RE)ERENCES *'+ B Patricelli # ?. # ?. ?ssogna # ?. Clasalaina # C. Cmmi and .. Sodini D <attori che influen3ano 0Iestra3ione dei lipidi da Semi decorticati di girasole E # La 1i!ista 0tliana Felle Sostan3e .rasse # !ol. 5- # '()( # PP '6- : '4% . *%+ B So #.. C. # and Fouglas .. Aacdonald # D /inetics of Oil Cxtraction from Canola ( 1apeseed ) E # Canadian J. Chem . Cng. !ol. -4 # '(,- # PP ,& : ,- .

*6+ B 2C1J?1F0J0 # C. # Publishing ;ouse # D Hegetable oils and <ats processing D # !olume 00 # 1OAC # '(,5 # PP %- : 5(4 . *4+ B S2P 2oard of Consultants and Cngineers # D Castor Oil and its Feri!ati!es E # Published by Small 2usiness Publications # 1oop Jagar # Felhi. *5+ B 2oucher # F. <. # J. C. 2rier # and J. O. Osburn # D Cxtraction of Oil <rom a Porous Solid E # ?merican 0nstitute of Chemical Cngineers # '(4% # PP (-) : ((6 . *-+ B Othmer # F. <. # and J. C. ?garwal # D Cxtraction of Soybeans B "heory and Aechanism E Chemical Cngineering progress # !ol. 5' # '(55 # PP 6)% 7 6),. *)+ B Coats # ;. 2. # and A. 1. >ingard # D Sol!ent Cxtraction 000 B "he Cffect of Particle Si3e on Cxtraction 1ate E # "he Journal of "he ?merican Oil ChemistsI Society # Aarch # '(5& # PP (6 : (5 . *,+ B ;aimour # J. A. # and Fib ?bu : <ara # D Cxtraction of Oli!e Oil from Oli!es Cxpression 1esidues E # *(+ B 0nternational Knion of Pure and ?pplied Chemistry # D Standard Aethods for the ?nalysis of Oils # <ats and Feri!ati!es E # -th Cd. # Part ' ( section 0 and 00 ) # Pergamon Press # Cngland # '()( .

NOTAT$ONS CL B Oil concentration in the oil free sol!ent ( g $ L ) # F B Cffecti!e diffusi!ity ( cm% $ min ) # /C B Aass transfer coefficient ( min:' ) # L B Solent !olume ( liter ) # m B mass ( g ) # r L B coefficient of determination. 1 B ratio of the sol!ent !olume to the solid mass ( ml$g )# t B "ime ( min ) # Su*scri+ts
d B Fiffusion stage # L B Sol!ent phase #

B 0ntial # s B Solid phase ( seed phase ) #

w B >ashing stage #

B <inal

&ist Of )i,ures

<igure ( ' ) B Sol!ent leaching experimental apparatus . <igure ( % ) B <itting of the experimental data using the models @ Patricelli ('()( ) and So ( '(,- ) # ( rpm G '-& # " G 6& C # 1 G 5# sol!entB hexane ) <igure ( 6 ) B <itting of the experimental data using the models @ Patricelli ('()( ) and So ( '(,- ) # ( rpm G %-& # " G 6& C # 1 G 5# sol!entB hexane ) <igure ( 4 ) B <itting of the experimental data using the models @ Patricelli ('()( ) and So ( '(,- ) # ( rpm G 6-& # " G 6& C # 1 G 5# sol!entB hexane) <igure ( 5 ) B <itting of the experimental data using the models @ Patricelli ('()( ) and So ( '(,- ) # ( rpm G %-& # " G 6& C # 1 G 4# sol!entB hexane) <igure ( - ) B <itting of the experimental data using the models @ Patricelli ('()( ) and So ( '(,- ) # ( rpm G %-& # " G 6& C # 1 G ,# sol!entB hexane) <igure ( ) ) B <itting of the experimental data using the models @ Patricelli ('()( ) and So ( '(,- ) # ( rpm G %-& # " G %& C # 1 G 5# sol!entB hexane) <igure ( , ) B <itting of the experimental data using the models @ Patricelli ('()( ) and So ( '(,- ) # ( rpm G %-& # " G 4& C # 1 G 5# sol!entB hexane) <igure ( ( ) B <itting of the experimental data using the models @ Patricelli ('()( ) and So ( '(,- ) # ( rpm G %-& # " G 6& C # 1 G 5# sol!entB erosene <igure ( '& ) B Cffect of mixing speed on the leaching of castor oil from milled castor seeds ( " G 6& C # 1 G 5 ) .

<igure ('') B Cffect of sol!ent:solid ratio on the leaching of castor oil from milled castor seeds ( " G 6& C # rpm G %-& ) <igure ( '% ) B Cffect of temperature on the leaching of castor oil from milled castor seeds ( rpm G %-& # 1 G 5 ) . <igure ('6) B Cffect of sol!ent type on castor oil leaching process .

Ta*les
"able ( ' ) B /inetic coefficients M C9ulibrium le!els for Sol!ent leaching of Castor Oil + % Sol!ent Sol!ent $ Solid Aixing Speed "emp. *! '& ratio ( rpm ) :' ( ml $ g ) ( C ) min n:;exane 4$' %-& 6& '4.,%( 5$' %-& 6& %%.&&& ,$' %-& 6& %4.&&& 5$' 6-& 6& 6%.'-5$' '-& 6& %'.&%4 5$' %-& 4& %6.5', 5$' %-& %& ').('5 /erosene 5$' %-& 6& 5'.&&&

*! '&
min &.464 &.-&& '.'65 '.%-5 &.%-, &.--6 &.',% (.56& :'

01

01

g$'&&g %.')45 %.&-5 '.--' %.'4% '.(&& 6.46&.((, 5.-'4

g$'&&g '.6&, &.)&% &.5,4 &.-%5 &.,-) %.'&4 &.)5% 6.%,-

% r &.(, &.(, &.(, '.&& '.&& '.&& '.&& &.(,

"able ( % ) B /inetic coefficients M C9ulibrium le!els for Sol!ent leaching of Castor Oil Aode + % d' % d% % Sol!ent Sol!ent $ Solid Aixing "emp. *! '& * ! '& *! '& ratio Speed (C ) :' :' :' ( ml $ g ) ( rpm ) min min min n:;exane 4$' 5$' ,$' 5$' 5$' 5$' 5$' 5$' %-& %-& %-& 6-& '-& %-& %-& %-& 6& 6& 6& 6& 6& 4& %& 6& -%.--& ,5.&&& ')&.&&& (5.,)& )&.&&& (&.&&& 6&.&&& ''&.&&& -.(') ''.%&% '-.%,4 ',.(%'&.&&& '5.54, '&.&&& '6.'&& &.%'% &.,-' '.&&& '.&&) &.'%' &.(&& &.'4' '.&&&

01

01

d'

01

d%

g$'&&g &.)-4 &.)6) &.%6( &.,&&.),( '.-&' &.5'4.'4&

g$'&&g '.)''.6-( '.566 '.44' '.%5% '.-&' &.5'( 4.55%

g$'&&g '.&&6 &.--& &.4)4 &.5%& &.)%%.66, &.)'5 &.%&,

/erosene

'.&& '.&& '.&& '.&& '.&& '.&& '.&& &.(,