CC BY
15
UDC 661.183.123.54.607
USING OF MODIFIED NANOCLAY AT BLEACHING OF THE NATURALIZED
SOY-BEAN OIL
2 * 1 2 1 * 1 Sh.Naseri , A.I.Yagubov , A.Alemi , Z.R.Agayeva , V.A.Ismailova ,
A.Fallahzadeh Abarghueeb 3
1 M.Nagiyev Institute of Catalysis and Inorganic Chemistry NAS of Azerbaijan
2
Department of Inorganic chemistry Faculty of chemistry University of Tabriz, Iran 3 ETKA Sciences and Technology Research Center, Tehran, Iran
rovshan_ismayilov83@mail.ru
Received 13.05.2015
Bleaching process is a critical stage in refining of vegetable oils. The used bleaching clay adsorbes metals, phosphatides, dye and soap in vegetable oils. The effect of nanoclay particles on practical properties of vegetable oils bleaching was investigated. For this aim the particles of nanoclay and its bleaching form have been used. Nanoparticles of the natural montmorillonite, modified quaternary ammonium salt and immodified montmorillonite have been added to bleaching clay and their effect has been investigated at bleaching soy-bean oil. The result showed, that the obtained mixture decreases amount of phosphatides in naturalized soy-bean oil greatly.
Keywords: nanoclay, vegetable oil, phosphatide, montmorillonite.
Introduction
Clays are widely applied in many fields such as polymernano-composites [1, 2], adsorbents for heavy metal ions [3, 4], catalysts [5], in photochemical reaction [6], ceramics [7], paper filling and coating [8], sensors and biosensors [9], due to their high specific surface area, chemical and mechanical stabilities, and a variety of surface and structural properties [10]. The most used clays as nano-adsorbents are montmo-rillonites/smectite group and kaolinite group clays. The smectite group refers to a family of non-metallic clays primarily composed of hydrated sodium, calcium and aluminium silicate, a group of monoclinic clay-like minerals with general formula of (Ca, Na, H)(Al, Mg, Fe, Zn)2(Si, Al)4O10(OH)2-nH2O. Smectite is a clay mineral having a 2:1 expanding crystal lattice. Its amorphous substitution gives the various types of smectite and causes a net permanent charge balanced by cations in such a manner that water may move between the sheets of the crystal lattice, giving a reversible cation exchange and very plastic properties. Membranes of the smectite group include the decahedral minerals montmorillonite, beidellite, nontronite, bentonite, and the trioctahedral mineral - hec-torite (Li-rich), saponite (Mg-rich), and sauco-
nite (Zn-rich). The basic structural unit is a layer consisting in two inward-pointing tetrahedral sheets with a central alumina octahedral sheet. The layers are continuous in the length and width directions, but the bonds between layers are weak and have excellent cleavage, allowing water and other molecules to enter between the layers causing expansion in the height direction [11].
The nanoclay, montmorillonite, and some modified nanoclays are used as sorbents for nonionic, anionic and cationic dyes. Among the different dye and clay structures, chemical and morphological as well as the sorption forces that play important role are different. The nanoclay could easily have a sorption capacity of more than 600 mg sorbate per gram of sorbent at a liquor-to-sorbent ratio of 100:1. Furthermore, it could have a sorption of 90% at an initial dye concentration of 6 g/L, or 60% based on the weight of the sorbent, indicating an extremely high dye affinity [12].
Experiments and methods
In this study, the nanoclay modified with quaternary ammonium salt (Closite 30B Southern Clay Products, Texas, USA) and nanoparticles of natural montmorillonite [Closite Na+ (Southern Clay Products, Texas, USA)] are used (Table 1, 2).
Table 1. Properties of the phosphatide
Phosphatide, ppm Yellow (Lovibond 51/4 in cell) Red (Lovibond 51/4 in cell) Acidity, mg KOH/g Soap, ppm
1418.4 50 6 0.07 15.2
Table 2. Nanoparticles of natural and modified montmorillonite
Physical Properties Closite Na+ Closite 30B
bulk density 0.3356 g/cC 0.3638 g/cC
loss on ignition 7.00% 30.00%
10% <= 2.00 ^m <= 2.00 ^m
particle size 50% <= 6.00 ^m <= 6.00 ^m
90% <= 13.0 ^m <= 13.0 ^m
modifier concentration, mq/100 g clay 92.6 90
Organic modifier - Methyltallow, è/s-2-hydroxyethyl quaternary ammonium bases
X-Ray Diffraction d-Spacing (001) 11.7 Â 18.5 Â
The ordinary bleaching clay is obtained from Iranian mineral company (Kanisazjam). They were created at an independent test lab using a mixer prepared samples been labeled based on weight percent of nanoclay added to the bleaching clay. Thirty specimens were made.
The naturalized soy-bean oil obtained from Ganjeh Roodbar oil factory. The samples then were analyzed using bleaching reaction with naturalized soy-bean oil.
Bleaching procedure carried out by AOCS method (Cc-8f-91). The measurement of pH and acidity of clay samples carried out by AOCS method (Cc-8f-91). Dye analysis of vegetable oil carried out by AOCS method
In vegetable oil, phosphatides, soap, heavy metals and dye rival for adsorption on the surface of bleaching clay. As one of these com-
(Cc-13c-50) and Lovibond PFX-j. The content of phosphatides in vegetable oil measured by AOCS method (Ca12-55). The content of soap in oil measured by Analysis British Standard.
Result and discussion
The properties of different composite formulations of bleaching clay and nanoparticles are given in Table 3. pH and moisture are important parameters in bleaching stage. When concentration of nanoparticles in bleaching clay increased the density of this composite (nanoclay and bleaching clay) reduced, so resulted in better adsorption of red dye and phosphatides in soy-bean oil.
pounds adsorbed on the surface of bleaching clay, its capacity for adsorption of the others will be reduced. The results show when phos-
Table 3. The properties of different composite formulations of bleaching clay and nanoparticles
Index Bleaching clay, % w Closite, Na+ % w Density, g/L pH (10% suspension, filtered) Moisture, 2h, 110c, % Acidity, mg KOH/g
N1 90 10 815 3.4 7.89 8.71
N2 80 20 786 3.7 7.44 5.78
N3 70 30 713 3.8 6.94 2.79
N4 90 10 819 1.8 9.36 34.84
N5 80 20 831.5 1.4 9.6 60.58
N6 70 30 794.6 1.1 10.8 86.72
N7 0 100 1041 1.1 19.7 277.62
N8 50 50 818.6 1.1 7.36 139.56
phatides and soap are adsorped other compounds adsorp poorly. In this study the bleaching clay modified with nanoclay Closite Na+
Table 4. Study the modified bleaching clay
It was shown that acid modification of montmorillonite generates materials with improved adsorption-structural characteristics and high adsorption capacity towards small nonpolar molecules. In N1, N2 and N3 composite formulas, density decreases as Na+ nanoclay content increases. The larger size and the higher density of the bleaching clay structures result in the slower rate of the reaction. The results demonstrated that using nanoparticles in bleaching process of soy-bean oil reduced phosphatides content of oil in comparison with bleaching clay. Among 13 nano formulation samples 9 formulas reduced phosphatides content in oil clearly. The results about 4 formulation were dramatic, because of phosphatide content in oil reduced to zero. The pH of clay are very important factor because in lower pH it is possible that the oil hydrolyzed and bleaching process failed. In Fig. 1 the reduced content of phosphatide in bleached oil is shown. Nine nano formulation of bleaching clay synthesis (N1, N2, N4, N5, N6, N8, B1, B3, B4) reduced content of phosphatide in oil is more than ordinary bleaching clay without any nanoparticles (K1).
The results of effect of nanocomposite bleaching clay on red dye in naturalized soybean oil are shown in Fig.2. As showed in
have more effect on the phosphatides adsorption (Table 4).
Fig. 2, the sample with 10% w/w, 20% w/w and 30% w/w of nanoclay Closite Na+ (N1, N2, and N3) have more effect on the reduction of red dye.
It is shown that adsorption of red dye depends on pH of bleaching clay. As pH increases adsorption of red dye also increases. The optimum value of pH for bleaching clay is between 1.8 and 3.8.
The adsorption of red dye decreases with increasing acidity of bleaching clay as showed in Fig. 3. The nano bleaching clay N1, N2, N3 are more effective for decreasing red dye of soy-bean oil. The value of red dye for this three nano formulae of bleaching clay were 5.5, 5.4 and 5.2 respectively while this parameter for ordinary bleaching clay reduced from 6 to 5.6.
Increasing of acidity of bleached soybean oil with nano bleaching clay in comparison with ordinary bleaching clay was lower. Four formulas N1, N2, N3 and N4 (with 8.71, 5.78, 2.79, 34.84 value of acidity respectively) increased the acidity of oil from 0.07 to 0.08, 0.07, 0.1 and 0.11 respectively whereas bleaching clay K1(with 14.05 value of acidity) increased the value of acidity of oil from 0.07 to 0.11.
Index Phosphatide, ppm Yellow (Lovibond 5 1/4 in cell) Red (Lovibond 5 1/4 in cell) Acidity, % oleic Soap, ppm
N1 0 50 5.5 0.08 0
N2 0 50 5.4 0.07 0
N3 848.1 50 5.2 0.1 0
N4 35.4 50 5.7 0.11 0
N5 4.5 50 6.4 0.13 0
N6 168.6 50 6.2 0.13 0
N7 572.4 70 8.7 0.18 0
N8 35.1 50 7 0.16 0
B1 13.2 50 5.5 0.12 0
B2 582.3 30 5.5 0.12 0
B3 361.8 50 6 0.14 0
B4 171 50 6 0.14 0
B5 1287 70 7 0.13 0
K1 382.2 40 5.6 0.11 0
1600 1400 1200 1000 aoo soo
400 200 o
I .1
s&r w
Fig l.The content of phosphatide in bleached soy-bean oil after treatment with different formula of bleaching clay.
10 9
S a
E
Fig 2. The red dye in bleached soybean oil after treatment with different formula of bleaching clay.
10 9
8
o -I-1-.-1-i-1-i—
O 2 4 6 B 1-0 12 14 16
Fig 3. The adsorption of red dye verses pH of bleaching clay.
Conclusion
This work concluded that nanoparticles may be useful for bleaching stage of vegetable oil. We consider two different nanoclay structures for bleaching soy-bean oil. The results show that adsorption of phosphatide red dye may be improved by using nanoclay. In comparison of the values of phosphatide red dye in bleached oil. Using nanoparticles shows superiority of the nanoclay composite with bleaching clay over the last one. We have shown that nanoclays are able to decrease the phosphatides of naturalized soy-bean oil dramatically.
Obtained results indicate that pH, moisture and acidity of bleaching clay plays important roles in bleaching process. We realized that the selection optimum pH is important in the performance of the bleaching process. The main conclusion of this study is that nanoparti-cles are a reliable material for the adsorption of compounds in vegetable oil. The results of different formulae of bleaching clay modified with nanoclay are gathered in Table 3. This study showed that with certain modifications the bleaching clay with only 20% w of nanoclay could decrease easily the content of phosphatides, dye and soap in soy-bean oil without increasing free fatty acids in bleached oil.
Reference
1. Fischer H. Polymer nanocomposites: from fundamental research to specific applications // Materials Sciences Engineering. 2003. No 23. P. 763-772.
2. Sinha Ray S., Okamoto M. Polymer layered silicate nanocomposites: a review from preparation to processing // Program Polymer Sciences. 2000. No 28. P. 1539-1641.
3. Bradl H.B. Adsorption of heavy metal ions on soils and soils constituents // J. Colloid Interface Sciences. 2004. No 27. P. 1-18.
4. Gil A., Gandia L.M., Vicente M.A. Recent advan-ces in the synthesis and catalytic applications of pillared clays // Catal. Rev. Sci. Eng. 2000. No 42. P. 145-212.
5. De Stefanis A., Toklinson A.A.G. Towards designing pillared clays for catalysts // Catalysys. Today. 2006. No 14. P. 126-141.
6. Shichi T., Takaqi K. Clay minerals as photochemical reaction fields // Journal Photochem. Photobio. C: Photochem. Rev. 2000. No 1. P. 113-130.
7. Burst F. Application of clay minerals in ceramics //Application Clay Sciences. 1991. No 5. P. 421-443.
8. Bundy W.M., Ishley J.N. Kaolin in paper filling and coating //Application Clay Sciences. 1991. No 5. P. 397-420.
9. Mousty C. Sensors and biosensors based on clay-modified electrodes // Application Clay Sciences. 2004. No 27. P.159-177.
10. Murray H.H. Overview - clay mineral applications // Application Clay Sciences. 2000. No 17. P. 207-221.
11. Bergaya F., Lagaly. General Introduction: Clays, clay minerals, and clay science. In: Bergaya F., Theng B. K. G., Lagaly G. (eds) Handbook of clay science. Elsevier, Academic Press., 2006. P. 118
12. Yang Y.Q., Han S.Y., Fan Q.Q. Nanoclay and modified nanoclay as sorbents for anionic, cationic and nonionic dyes // Textile Res. Journal. 2005. No 75. P. 622-627.
TOBiiLO§DiRlLMi§ SOYA YAGLARININ AGARDILMA PROSESiNDO MODiFiKASiYA OLUNMU§
NANOGILLORiN iSTiFADOSi
Ç.Naseri, O.i.Yaqubov, A.Alami, Z.R.Agayeva, V.O.ismayilova, O.Falahzada
Agardirilma prosesi bitki yaglarinin tamizlanmasi prosesinin bôhran marhalasidir. Istifada olunan agardici gil bitki yaglarindan metallari, fosfatidlari, boyalari va sabunlari adsorbsiya edir. Tabiilaçdirilmiç soya yaglarinin effektivliyina modifikasiya olunmuç nanogillarin tasiri ôyranilmiçdir. Tadqiqatlar zamani muayyan olunmuçdur ki, sorbentlarlarin dôrdlu ammonium duzlarinin nanohissaciklari ila modifikasiya olunmasi tamizlanmiç soya yaglarinda olan fosfatidlarin miqdarinin ahamiyyatli daracada azalmasina qatirib çixarir.
Açar sozlzr: nanogilbr, bitki yaglari, fosfatid, montmorillonit.
ИСПОЛЬЗОВАНИЕ МОДИФИЦИРОВАННОЙ НАНОГЛИНЫ В ОТБЕЛИВАНИИ НАТУРАЛИЗОВАННОГО СОЕВОГО МАСЛА
Ш.Насери, А.И.Ягубов, А.Алеми, З.Р.Агаева, В.А.Исмайлова, А.Фаллахзаде
Процесс отбеливания - это критическая стадия рафинирования растительных масел. Используемая отбеливающая глина адсорбирует металлы, фосфатиды, краски и мыло в растительных маслах. Исследован эффект частиц наноглины на практические свойства растительных масел при их отбеливании. Для этой цели использованы частицы наноглины и ее отбеливающей формы. Наночастицы природного монтмориллонита, модифицированного четвертичной солью аммония, и немодифицированного монтмориллонита были добавлены в отбеливающую глину и исследован их эффект при отбеливании соевого масла. Результаты показали, что полученная смесь значительно уменьшает количество фосфатидов в натурализованном соевом масле.
Ключевые слова: наноглина, растительное масло, фосфатид, монтмориллонит.
