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Journal of Global Pharma Technology Purification, Beneficiation and

Activation of Iraqi Attapulgite Clay Mineral

Article  in  Journal of Global Pharma Technology · November 2019

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 ISSN: 0975 -8542
Journal of Global Pharma Technology
Available Online at: www.jgpt.co.in

RESEARCH ARTICLE

Purification, Beneficiation and Activation of Iraqi

Attapulgite Clay Mineral
Nadhum Gharb Taher , Mohammed H. Abdul Latif

Department of Chemistry, College of Education for Pure Science Ibn Al Haitham,

University of Baghdad , Adhamiya, Al- Dilal Square, Baghdad, Iraq.

*Corresponding Author: Nadhum Gharb Taher

Abstract

This study aimed to obtain a pure activated Attapulgite mineral to use it as adsorption surface in our
search, because of its importance in removing impurities, desulfurization, decolorizing, neutralizing, and
deodorizing of petroleum fuel. The large specific surface area and high cation exchange capacity of
Attapulgite make it suitable in our work. However, the adsorption capacity of natural Attapulgite is
limited, new activated pure Attapulgite clay was synthesized by purification and beneficiation
Attapulgite to increase its ability to use in our search and other various fields, particularly in the
petroleum refining. The pure activated calcined Attapulgite characterized by FT-IR spectroscopy, X-ray
diffraction (XRD), and scanning electron microscopy (SEM). Attapulgite mineral was purified by
floatation with the dispersed swelled sodium methyl acrylate granules leaving other impurities of clay
mineral and sand in the bottom of the vessel. Therefore many peaks in FT-IR spectrum were disappeared
comparing with the FT-IR spectrum of crud material. The disappearance of calcium carbonate peaks at
(29.3556) 2 Ɵ was observed due to the purification of Attapulgite from other mineral impurities using
sodium methyl acrylate, while the peaks of the Attapulgite remained clear. SEM images of pure
activated Attapulgite show a high resolution with an accurate vision of needle- shaped structure.

Keywords: Desulfurization; Beneficiation; Attapulgite; Adsorption; Surface.

Introduction
Attapulgite or Polygorskite is needle-like coloring abilities, temperature resistant and
natural clay mineral Figure 1; consist of Possesses plastic & adhesive characteristics.
magnesium-aluminum silicate mineral. Attapulgite is of a laminated chain structure
Polygorskite is salt gel, fuller's earth, and as seen in Figure 3, [1] where significant
activated natural clay. Attapulgite of a substitution of Mg+2 by Al+3 and Fe+3 take
molecular formula is: [(OH2)4 (Mg. Al)5 (OH)2 place in the octahedral position and Ca+2,
Si8 O20] 4H2O Figure 2, exhibit a good Na+ and K+ take place as interlayer cations
dispersion colloidal properties, high [2, 3].
adsorbing capacities, alkaline resistant, de

Figure 1: Attapulgite Image under high resolution SEM

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 Nadhum Gharb Taher & Mohammed H. Abdul Latif| Journal of Global Pharma Technology | 2019| Vol. 11| Issue 07 (Suppl.) |870-877

Figure 2: Structure of Attapulgite Clay

Figure 3: Attapulgite chain structure

Attapulgite uses divided into two broad 53 colloidal and non-colloidal, table 1 represents
categories: these uses [4].
Table 1: Uses of Attapulgite clay mineral
Colloidal Non Colloidal
1 Oil-base and water-base foundry sand binders 1 Petroleum refining, decolorizing, neutralizing,
brightening, desulfurization, deodorizing
2 Adhesive viscosity control 2 Vegetable oils and animal fats neutralizing,
decolorizing, deodorizing
3 Oil well drilling mud 3 Carrier for granular and powdered agricultural
chemicals (insecticides, herbicides, etc.)
4 Latex paint thickener and gelling agent 4 Pharmaceutical intestinal absorbent
5 Pharmaceutical thickener and adsorbent 5 Floor absorbents
6 Liquid suspension fertilizers 6 Animal bedding, pet litter
7 Polishes— suspending agent for abrasives 7 Flow ability additive to dry fire extinguisher
powders
8 Wax emulsion stabilizer 8 Catalytic applications (no carbon required papers,
olefin polymerization, etc.)
9 Metal drawing lubricants— suspending agent 9 Anti-caking agent
10 Laundry washing powders 10 Chromatographic adsorbent
11 Bonding agent for granulation of powders 11 Drying of oils

Attapulgite is widely distributed in Iraq, take governorate was used to produce high
place in many rock units, like Digma reactivity Attapulgite [6]. The origin of
Formation (Akashat area) which is one of the Attapulgite, in these formations, is of marine
important Attapulgite-rich Formations in sedimentary and almost always correlating
Iraq, [5] also Attapulgite clays from Tar AL- with Montmorillonite clay mineral [7].
Najaf (Injana) region in AL- Najaf

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The montmorillonite correlating with the Experimental

Attapulgite-bearing rocks of these
Materials
Formations is of Calcium base which is non-
swelling clay therefore our study is important Najaf Iraqi Attapulgite-montmorillonite clay
to prepare a pure and active Attapulgite clay stone used in the present work was obtained
mineral free of Ca- Montmorillonite by from the General Company for Geological
creating a new and easy method for
Purification, Beneficiation and Activation of Survey and Mining in Baghdad, Iraq. This
Iraqi Attapulgite clay mineral. crude Attapulgite-Montmorillonite claystone
is gray italics to green in color; Table 2 shows
chemical analysis of crude Attapulgite-
Montmorillonite claystone sample.

Table 2: Chemical analysis of crude Attapulgite – Montmorillonite claystone sample

Compound SiO2 Al2O3 Fe2O3 CaO MgO SO3 % L.O.I Total
Wt. % 49.0 12.6 6.2 6.2 6.0 1.5 11.6 93.1

Clay Sample was sieved to yield particle size The second step involves activation of 15%
equal to75µm and 250 µm, dried in an Attapulgite-montmorillonite slurry in
electric oven at 100 ºC for 24 h., and stored in distilled water (prepared from the first step
a desiccator for use. Chemicals were dried clay), by treatment with H- form
purchased from Fluka-BDH Chemicals. Amber light orange ion exchange at the
Distilled and deionized water with a molar ratio of 1:1, followed by agitation for 24
conductivity value of 1.5 x 10-5 S Cm-1 was h. at 150 rpm and 60 ºC using thermo- stated
used. shaker bath (Alba Tch.). Clay suspension was
separated from Amber light orange ion
Instruments exchange granules using 75µm sieve.
FT-IR instrument (Shimadzu FT-IR
The resulting solid was separated by
Spectrometer-30000:1/IRAFF); Thermostatic
centrifugation washed five times with
Shaker Bath [GFL (D-3006), Fed – Rep. of
deionized water and dried at 100 ºC for 24
Germany]; Centrifuge (JANETZI-T5,
hour. The third step involves the separation
Germany, 3000 rpm); X-ray diffraction
of the Attapulgite clay mineral from the
(Shimadzu X-ray Diffraction meter 04-XRD-
associated Montmorillonite clay by addition
6000); Scanning Electron Microscope, (SEM
of sodium methyl acrylate as a chemical
Micrographs VEGA3 TESCAN); Electric
dispersant to 15 % Attapulgite-
Balance; (Sartorius Lab-BL 210 S, Germany
montmorillonite slurry in distilled water
± 0.0001g); Oven Equipment LTD, Green
(prepared from the second step dried clay),
Field, NR OLDJAM, (20-360 C°) furnace;
selectively disperse discrete, individual
Forth Flotation cell; and Granulating
particles of Attapulgite while liberating other
Machine (GK Dry Granulating Machine).
non-Attapulgite minerals such as
Preparation of activated and Pure Montmorillonite, Sepiolite, Bentonite,
Attapulgite Calcium Carbonate, Silica and Kaolin, from
in between the Attapulgite Bundles [8].
Aqueous slurry containing 15% solid raw
claystone was initially prepared using Najaf Then resulting solid was separated by
Iraqi Attapulgite-montmorillonite raw centrifugation washed five times with
claystone sample. Homogenized clay slurry deionized water and dried at 100 ºC for 24
was prepared using high impeller speed 2500 hour after shaping by a granulating Machin
rpm for 1 h. and was advantaged to increase to 1 and 2 mm diameter granules. Finally,
its Attapulgite – montmorillonite content and the dried pure H-Form Attapulgite granule
cation exchange capacity (CEC) by attrition- was calcined at 900 ºC using Muffle Furnace
scrubbing using Flotation Cell. The resulting to be converted into non-dissoluble granules
solid was separated by centrifugation, in aqueous and organic solutions [9].
washed five times with deionized water and
dried at 100 ºC for 24 hour.

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Result and Discussion FT-IR spectrums of Attapulgite samples were

shown in Figure 4.
FT-IR Characterization of Attapulgite
Clay Samples

A: crude Attapulgite B: activated Attapulgite

C: pure activated Attapulgite D: pure activated calcined Attapulgite

Figure 4: FT-IR of Attapulgite crude (A); activated Attapulgite (B); pure activated Attapulgite (C); and pure activated
calcined Attapulgite

FT-IR Analysis of Crude Attapulgite & Mg); (3545 cm-1) refer to H2O coordinated;
Sample (1647 cm-1) refer to H2O adsorbed water
The important peaks of active groups in bending ); (1531 cm-1) refer to Al2O3
Attapulgite crude FT-IR spectrum was stretching; (1100 cm-1) refer to Si-O-Si
involved in table 3, represent (3743cm-1), & bending; (974 cm-1 ) refer to (O-SiO3)
(3641 cm-1) peaks that refer to O-H bonded stretching; (910 cm-1 ) refer to (M-OH; M;
with H stretching; (3618cm -1) refer to O-H metal (bending ); ( 860 ,820 cm-1) refer to Si-
bonded with metal stretching (metal: Al, Fe, OH; and (702cm-1) refer to metal with O as
oxide.
Table 3: FT-IR spectrum of Attapulgite crude
Group Mode of Vibration νcm-1
-OH Stretching 3743
-OH Stretching 3618
-OH Stretching 3641
H-O-H H2O coordinated 3545
H-O-H H-O-H adsorbed 1647
Al2O3 Stretching 1531
Si-O-Si (Al) Bending 1100
Si-O-Si (Al) Bending 974
M-OH Stretching 910
Si-OH Bending 860,820
M-O Stretching 702

FT-IR Analysis of Activated Attapulgite again due to presence them in structure of

Sample mineral, but more strong and sharp because
the purification removed the impurities and
The peaks (3747, 3641, 3618, 1531, 1100,
sands from minerals. Due to increase of space
974, 910, 860 & 820 cm-1) bands appears
among layers and replaced cations by H+ ions,

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 Nadhum Gharb Taher & Mohammed H. Abdul Latif| Journal of Global Pharma Technology | 2019| Vol. 11| Issue 07 (Suppl.) |870-877

make the account of water increases because entrance the water. Mg-O appears because of
of swelling; (3300 cm-1) refer to O-H (H2O) Montmorillonite prefund with Attapulgite M-
normal polymeric (stretching) as evidence of O at (719cm-1) like Al+3, Fe+3& Mg+2.

Table 4: FT-IR spectrum of activated Attapulgite

Group Mode of Vibration νcm-1
-OH Stretching (str.) 3743
-OH Stretching (str.) 3618
-OH Stretching(str.) 3641
H-O-H H2O coordinated(m) 3545
O-H Normal polymeric(stretching)(str.) 3300
-OH H2O coordinated water (bending)( str.) 1647
Al2O3 Stretching(m) 1531
Si-O-Si(Al) Bending (m) 1100
Si-O-Si(Al) Bending(str.) 974
M-OH Stretching(w,) 910
Si-OH Bending (m) 860,820
M-O Stretching (w) 702

FT-IR Analysis of Pure activated material. Some peaks become strong because
Attapulgite Samples the structural composition of mineral did not
change. (923 cm-1) due to SiH3; (806, 820 &
Due to addition of sodium methyl acrylate
873cm-1) for Si-O; (3545 cm-1) due to
Attapulgite mineral was purified by
Coordinated water stretching O-H (H2O);
floatation with the dispersed swelled sodium
(3219cm-1) for H-O-H; bonded( stretching,(
methyl acrylate granules leaving other
1662,1650 &1629cm-1) for Coordinated and
impurities of clay mineral and sand in the
absorbed water H -O-H.(1541cm-1) due to
bottom of the vessel. Therefore many peaks
Al2O3 bending; (1068cm-1) for Mg-O bending;
in FT-IR spectrum were disappeared
(719cm-1) due to M-O bending.
comparing with the FT-IR spectrum of crud

Table 5: FT-IR-spectrum for pure activated Attapulgite

Group Mode of Vibration νcm-1
O-H( H2O) Coordinated water ( stretching) 3545
H-O-H Stretching 3219
H-O-H crystalation lattice water 3097
H-O-H Coordinated and absorbed water 1629,1650,1662
Al2O3 bending 1541
Si Silicon 1604
O-SiO3 Asymmetric )Bending0 1120
Si-O-Si Stretching 1159
Mg-O bending 1068
-OH bending 1020
O-SiO3 bending 977
SiH3 bending 923
Si-OH bending 806 ,820 ,873
M-O bending 719

FT-IR Analysis of Pure activated calcine 900 C° ; (1022.27cm-1) for (Si-O) group become
Attapulgite Samples stronger and bordered due to calcining
operation. (1539cm-1) of Al2O3 bending was
Peaks appeared in FT-IR chart due to
small because of water loos due to calcining.
calcining. Most of compounds specially
The above explanations indicate that a pure
hydroxides of metals converted to oxides,
activated calcined Attapulgite was obtained
coordinated and adsorbed water disappeared
as shown in Table 6.
because of calcining at high temperature 850-

Table 6: FT-IR spectrum of pure activated calcine Attapulgite

Group Mode of Vibration νcm-1
Al2O3 Bending (m) 1539
Si-O-Si Stretching (str.) 1022.27
SiH3 Twisting (m) 692

Powder X-ray diffraction Powder X-Ray Diffraction of Attapulgite

Characterization of Attapulgite clay crude
Samples

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Figure 5: X-ray of Attapulgite crude

Table 7: X - ray diffraction peaks of Attapulgite crud

Compound or group 2Ɵ (deg) d(A) I (C/Sec.)
Attapulgite 8.5138 10.37740 109
Attapulgite 20.8896 4.24958 36
Quartz 26.6684 3.33997 136
Calcite 29.4448 3.03105 742

The peaks of Attapulgite appear at (8.5138, The comparison between the crude and the
20.8896)2Ɵ (deg.)); Quartz at (26.6684 2Ɵ activated acetylate shows an increase in the
(deg.); Calcite at (29.4448)2Ɵ (deg.). X- Ray absorption intensity of Attapulgite at
diffraction spectrum shown in Figure5. Peaks (8.28819; & 6977) 2Ɵ in X-ray diffraction
in Table (7) with location and severity, [91, spectra, due to the removal of impurities and
127-128].The peaks explain presence of high band gape due to high swelling, as
Attapulgite, quartz and calcite. shown in table 8, and Figure 6.

Powder X-ray Diffraction of activated

Attapulgite

Figure 6: X-ray of pure activated Attapulgite

Table 8: x- ray diffraction spectrum peaks of activated Attapulgite

Compound or group 2Ɵ (deg) d(A) I (C/Sec.)
Attapulgite 8.2880 10.65961 153
Attapulgite 19.6977 4.50337 91
Quartize 26.5660 3.35261 174
Calcite 29.3556 3.04006 235

PXRD of a Pure activated Attapulgite mineral impurities using sodium methyl

acrylate, while the peaks of the Attapulgite
The disappearance of calcium carbonate
remained clear, as shown Figure 7, and Table
peaks at (29.3556) 2 Ɵ was observed due to
9.
the purification of Attapulgite from other

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 Nadhum Gharb Taher & Mohammed H. Abdul Latif| Journal of Global Pharma Technology | 2019| Vol. 11| Issue 07 (Suppl.) |870-877

Figure 7:X-ray of pure activated Attapulgite

Table 9: x- ray diffraction spectrum peaks of pure activated Attapulgite

Compound or group 2Ɵ (deg) d(A) I (C/Sec.)
Attapulgite 8.4347 10.47454 24
Attapulgite 8.6720 10.18844 19
Quartize 26.5584 3.35356 100

PXRD of a pure activated calcined due to calcing process to high temperatures

Attapulgite range 850-950 Co that leds to shrinking of the
band gape of Attapulgite clay mineral, as
The Attapulgite peaks at (8.4347; 19.3471; &
shown in Figure 8 and Table 10.
20. 7722) 2Ɵ have a low intensity absorption

Figure 8:X-ray of pure activated calcine Attapulgite

Table 10: x- ray diffraction spectrum peaks of pure activated calcined Attapulgite
Compound or group 2Ɵ (deg) d(A) I (C/Sec.)
Attapulgite 8.4347 10.47454 24
Attapulgite 19.3471 3.04092 50
Attapulgite 20. 7722 4.27279 24
Quartz 26.5584 3.35356 100

Scanning Electron Microscopy (SEM) activated Attapulgite show a high resolution

Characterization of Attapulgite clay with an accurate vision of needle- shaped
Samples structure, due to the active purification
method using sodium methyl acrylate. The
SEM images of low and high magnification
calcined pure activated Attapulgite SEM
Figure 12 (1a, 1b, 1c, &1d) of initiated H -
images Figure 12 (3a, 3b, 3c, &3d) show that
form Attapulgite show a normal
the sharpness of needle- shaped structure
characteristic needle- shaped structure of
was diminished due to the loosing of the
Attapulgite Clay mineral, while in Figure 12
water of crystal lattice.
(2a, 2b, 2c, &2d) the SEM images of pure

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 Nadhum Gharb Taher & Mohammed H. Abdul Latif| Journal of Global Pharma Technology | 2019| Vol. 11| Issue 07 (Suppl.) |870-877

Figure 12: SEM images 1a, 1b, 1c, &1d of initiated H - form Attapulgite; 2a, 2b, 2c, 2d SEM images of pure activated
Attapulgite; 3a,3b,3c, 3d SEM images of calcined pure activated Attapulgite

Conclusion desulfurization, decolorizing, neutralizing,

and deodorizing of petroleum fuel and other
A new and efficient method was applied in
uses.
our search lead to having high percent active
H-form clay mineral and low percent of sand Acknowledgement
and impurities. Also applying a good
puplished method of purification of Best regards to the General Company for
attapulgite clay mineral [8] using sodium Geological Survey and Mining in Baghdad,
methyl acrylate increas the purity of Iraq who brought us the studied samples.
Attapulgite clay mineral, and this is our goal Also we would like to acknowledge Dean of
in benification of Attapulgite to increase its the Faculty of Education Ibn al-Haitham,
efficiency in in removing impurities, Chemistry, department for their financial
support.

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