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Journal of Industrial and Engineering Chemistry xxx (2014) xxx–xxx

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

2 Application of Iranian nano-porous Ca-bentonite for recovery of

3 waste lubricant oil by distillation and adsorption techniques
4 Q1 Shiva Salem a, Amin Salem b,c,*, Aylin Agha Babaei d
5 a
Faculty of Chemical Engineering, Urmia University of Technology, Urmia, Iran
6 b
Mineral Processing Research Center, Chemical Engineering Department, Sahand University of Technology, Tabriz, Iran
7 c
Center of Excellence for Color Science and Technology, Tehran, Iran
8 d
Faculty of Engineering, Islamic Azad University South Tehran Branch, Tehran, Iran

A R T I C L E I N F O A B S T R A C T

Article history: The nano-porous adsorbents were initially produced by acid treatment of natural clay. The effects of
Received 9 February 2014 some important factors such as acid type, concentration and residence time were evaluated on porous
Accepted 4 August 2014 structure of adsorbent. A reduction about 2.7 Å was observed in the distance of montmorillonite layers
Available online xxx
due to replacement of hydrogen ions in the presence of sulfuric acid. The number of nano-pores, 12 nm,
was preferable for removal of contaminations from spent engine oil, depending on the activation agent
Keywords: type in the treatment process. The results are very promising for reduction of adsorbent content in the
Waste lubricant oil
regeneration of waste lubricant oil. Q3
Distillation
Adsorption
ß 2014 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering
Bentonite Chemistry.
Acidification
Nano-porous

9
10 Introduction these variations in the oil characteristics, the metal particles are 28
deposited in the oil. As time passes, the engine oil loses the 29
11 Engine oil is an important lubricant that is extensively used in functional properties and it must be replaced with fresh oil. 30
12 the cars for lubrication, cooling and sealing of motor. The chemical The contaminants in waste oil can induce a variety of diseases in 31
13 analysis of lubricant oil depends on the source of crude oil and humans through inhalation, ingestion and skin contact. The waste 32
14 manufacturing method. The technical characteristics of oil are oil causes different type of illness, especially skin cancer. These 33
15 controlled by blending base oil with a few percent polymers such effects can be related to the presence of toxic materials. 34
16 as polyalphaolefines and polyisobutene [1,2]. Moreover, the other Particularly harmful metals that remain in the waste oil include 35
17 additives are used in composition of engine oil to neutralize acids lead, cadmium and chromium. Some of the impurities are formed 36
18 generated during the combustion and reduce corrosion [1]. by incomplete combustion of organic matter. Combustion of fuel 37
19 Though, the modern cars have only a very small loss of oil under containing carbon and chlorine can produce a wide range of 38
20 normal operation condition, a certain amount of lubricant is organo-chlorine compounds. The pollution of natural water, 39
21 degraded, limiting the life time of oil consequently. accumulation in the agriculture products and foods result in 40
22 The waste oil is contaminated by impurities obtained from adverse effects on human health [4]. 41
23 undesirable oxidation product, sediment, metallic wear particles Due to the high cost of crude oil, the countries try to find out the 42
24 and water, degraded additive and hazardous substances from lead alternative ways for fuel production. Thus, there is a great scope to 43
25 compound [3]. During operation of engine, the oil temperature manufacture fuel from waste engine oil which would help to 44
26 increases leading to degradation and change in the important decrease environmental problems, save waste oil disposal fees and 45
27 properties such as density, viscosity, flash point, etc. Regardless of reduce burden of fuel import [5,6]. By considering the quantity of 46
waste oil produced daily in the world, it is necessary to develop the 47
recovery processes. The engine oil is a very important material and 48
the recovery process for recycling of oil is an efficient technique [7]. 49
* Corresponding author at: Mineral Processing Research Center, Chemical
On comparing characteristics of refined base oil with waste, it is 50
Engineering Department, Sahand University of Technology, Tabriz, Iran.
observed that the recovery of used oil is responsible with respect to 51
Q2 Tel.: +98 4123459159; fax: +98 4123454335..
E-mail address: salem@sut.ac.ir (A. Salem). producing fuel. Recovery of waste engine oil is a regeneration 52

http://dx.doi.org/10.1016/j.jiec.2014.08.009
1226-086X/ß 2014 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering Chemistry.

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53 process in which the obtained oil can be used again. The choice of technical applicability and cost effectiveness are two key factors in 119
54 regeneration technique to achieve base oil is determined by the the selection of suitable adsorbent for treating waste oil. 120
55 nature of waste, cost and environmental considerations. Usually, Calcium bentonite is widely used in clarifying and purification 121
56 both mechanical and physico-chemical processes are required for of liquids such as liquors and oils due to their large specific surface 122
57 deep purification. The physical method includes removal of dirt, area. This material is preferred to use as an adsorbent because of its 123
58 sand and metal particles. The centrifugation, settling and filtra- porous structure and maintaining impurities. The properties of 124
59 tions are classified into mechanical techniques. Regarding physico- bentonite are function of montmorillonite amount which deter- 125
60 chemical, many advance methods such as supercritical separation mines quality of raw material as well as the specific surface area 126
61 [8], microwave pyrolysis [9,10] and catalytic process [11] can be [29]. Also, the other crystals, which exist in natural bentonite such 127
62 used for the removal of toxic materials from used oil. All these as cristobalite and opal CT, influence the adsorption capacity. The 128
63 procedures have significant disadvantages because of incomplete control of bentonite composition is necessary to get reliable 129
64 removal, high energy requirements and inapplicability in the performance in the industrial applications. The montmorillonite 130
65 industrial scale. These techniques also have different yield and structure is classified as dioctahedral, having two-thirds of 131
66 product quality, construction and operational cost. octahedral sites occupied by trivalent cations. The charge of 132
67 Waste engine oil usually is collected in garages. In some cases dioctahedral montmorillonite is originated from the substitution 133
68 gasoline is used for cleaning the transmission parts. Therefore, of Mg2+ in the octahedral sheet. The idealized structural formula 134
69 mixing gasoline with waste oil into the same container is for montmorillonite is M+ynH2O(Al2yMgy)Si4O10, where M is a 135
70 unavoidable. Even small amounts of gasoline or other solvents cation [30]. The negative charge is balanced by cations intercalated 136
71 may result in a low flash point and increase in the explosion risk between structural units. These cations may be alkali earth ions 137
72 during refining process. Before storing waste oil in tank, the water such as Ca2+ or the alkaline metals such as Na+. When Ca2+ cations 138
73 content, solids, flash and pour points, etc should be tested. are exclusively exchanged in montmorillonite, the clay is known as 139
74 Distillation, solvent extraction, adsorption and hydro-treating Ca-montmorillonite. 140
75 are preferred process because of high efficiency and low cost as The application of bentonites in production of selective 141
76 well as applicability in practice compared to advance techniques adsorbents, bleaching earth, catalyst beds, carbonless copy paper 142
77 [11]. Optimization of recovery factors should be considered to and medication depends on the pore structure of montmorillonite. 143
78 achieve either maximum sludge removal or minimum oil losses. If the pore diameters are smaller than 2 nm, these are called micro- 144
79 Water is removed from the waste oil by dehydration. Thus, the pores. If their sizes are between 2 and 50 nm, these are called 145
80 waste oil is distilled up to 100 8C. The vacuum distillation is used to meso-pores. Also, the material is named macro-porous if their sizes 146
81 eliminate the light hydrocarbons. The pre-treatment process for are larger than 50 nm. The adsorption capacity of the macro- 147
82 refining waste oil consists of two steps. In the first step water and porous materials is at a negligible level compared to that for the 148
83 light hydrocarbons are evaporated. After this step the dehydrated micro- and meso-porous adsorbents [31]. 149
84 oil is treated by vacuum distillation [7]. The most commercial used process for manufacturing Ca- 150
85 Traditionally, the automobile waste oil can be refined through bentonite with high specific surface area is acid treatment. The 151
86 vacuum distillation, acid and bleaching treatment [12,13]. As the activated bentonites are usually used as an adsorbent in the above 152
87 chemical treatment creates environmental problems, distillation, applications [32]. Activation is the chemical treatment applied to 153
88 adsorption and solvent extraction were proposed as alternate certain types of clay to develop their capacity to absorb coloring 154
89 methods. The solvent extraction treatment has received consider- matters and other impurities in the oils. The acid treatment of 155
90 able attention in recent years, because it overcomes the problems bentonite is carried out in a continuous stirred tank reactor at low 156
91 associated with acid sludge produced from chemical treatment. temperatures between 70 and 110 8C. During the activation 157
92 Solvent could be recovered by distillation, but the regeneration process, considerable amount of Ca2+ located between the layers 158
93 process is expensive and huge content of liquid should be were substituted by H+ [33]. This variation in montmorillonite 159
94 Q4 distillated to separate oil and solvent. Recently, waste oil has layers leads to significant changes in cation exchange capacity, 160
95 been refined by vacuum distillation with chemical treatment or CEC. Also, the specific surface area of bentonite can be affected by 161
96 clay adsorption due to low manufacturing cost [13]. acid solution due to decomposition of clay mineral structure. As 162
97 The characteristics of refined base oil obtained by vacuum bentonite is held in the acid solutions, the pores are developed 163
98 distillation and solvent extraction showed that these processes are within the clay microstructure [33]. The formation of new pores 164
99 good techniques for the removal of contaminants from used oil and allows increasing the specific surface area compared to its original 165
100 to enhance the desired properties [14,15]. The performance of 2- value [31]. As activation progresses, Al3+, Mg2+and Fe3+ leave the 166
101 propanol, 1-butanol and methyl-ethyl-ketone, MEK, in recycling octahedral layers and the cationic spaces remain empty [34]. 167
102 used oil was evaluated experimentally [16–18]. The results show Because of the favorable physical–chemical characteristics, the 168
103 that the solvent extraction technique is efficient process in activated bentonite is widely used in regeneration of waste 169
104 recovery of waste oil. The lowest percent oil loss as well as the lubricating oils. 170
105 best performance was achieved by the use of MEK. Extraction by The commercial interest in treatment of waste engine oil is 171
106 MEK and n-hexane followed by adsorption on magnesite gives the accompanied by a scarcity of knowledge about relationship 172
107 lowest color index oil. This system however uses two solvents and between bentonite activation factors and adsorption in recovery 173
108 thus requires two solvent recovery steps [19,20]. The color of oil is process. Although it is possible to find in the literature several 174
109 related to the nitrogen, sulfur and oxygen compounds and papers on used oil treatment as explained above, they are mainly 175
110 impurity fractions. The amounts of saturated compounds are focused on processing feasibility of different techniques and 176
111 increased due to hydro-treating of oil and this process can be adsorbents. The relationship between the activation factors and Q5 177
112 considered as final stage for stabilization the color of product [13]. technological properties of refined oil has been less well-studied, 178
113 Several materials have been used for regeneration of waste as the research in this field is focused on yield and efficiency of 179
114 engine oil as an adsorbent [21,22] such as magnesite [19], silica gel different low cost adsorbents. The effect of activation factors on 180
115 [23], charcoal [24], date palm kernel powder [25], kaolin [26] and technological properties of oil refined by distillation and adsorp- 181
116 natural and activated bentonites [27,28]. It is important to note tion process has not been previously investigated, leaving 182
117 that the removal efficiency of low cost adsorbents depends on the significant opportunities for research in this area. The present 183
118 material characteristics and surface modification. Overall, the work is part of a more extensive study with two main objectives. 184

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185 First, is to establish the effect of activation factors on physical and The adsorption ratio was determined from the amounts of 248
186 technological characteristics of Iranian Ca-bentonite and, second, MB need to reach the end point for activated and natural clays 249
187 to study the effect of activation factors on the regenerated oil [36]. 250
188 characteristics. For this purpose, it is very important to have In order to characterize the chemical composition of natural 251
189 knowledge about the behavior of natural bentonite during acid and activated clays, the inductive coupled plasma atomic emission 252
190 treatment. With this aim, the following criteria were considered. spectroscopy (Model 785, Varian Inc, Santa Clara, CA, USA) was 253
191 The selected natural adsorbent is a conventional composition that applied. The crystalline phase evaluation was carried out by X-ray 254
192 is applied by Iranian oil recovery factories without activation. From diffraction analysis using a diffractometer (Model D-5000, 255
193 the environmental point of view, the increase in content of used Siemens, Karlsruhe, Germany) with Cu-Ka radiation. The molecu- 256
194 adsorbent has a high hazardous potential. The optimization of lar vibrations of the resulting powders were evaluated by Fourier 257
195 acidification process should lead to the minimum consumption of transform infrared spectroscopy (Model Unicam Mattson 1000, 258
196 adsorbent. For this reason, the natural bentonite was activated Philips, Almelo, The Netherlands). The specific surface area, pore 259
197 with different concentrations of nitric and sulfuric acids. Also, the volume and average pore size of powders were measured from 260
198 effect of residence time was evaluated on activation and low-temperature nitrogen adsorption isotherms, using a Quanta- 261
199 regeneration processes. chrome instrument (Model Chem-BET 3000, Boynton Beach, FL, 262
USA). 263
200 Experimental
Distillation of waste engine oil 264
201 Clay activation process
Waste motor lubricating oil was collected from different local 265
202 The natural clay used in this study is from Soltaniyeh situated garages and service stations in Tabriz city. The lubricating oils of 266
203 on the highlands in the Western region of Iran. Soltaniyeh is a cars were changed after at least 6000 km in use and mixed in a 267
204 district in Abhar county, Zanjan province. The raw material, which single container, industrially. It was stored for several days for 268
205 is widely used as a bleaching earth in Iranian food and petroleum sedimentation of suspended particles by gravity. Waste oil 269
206 industries, was procured in ground form with the maximum grain treatment using dehydration and distillation causes the removal 270
207 size of 75 mm. The activation process was carried out in a small- of volatiles at low temperatures. Distillation is adequate to produce 271
208 scale batch setup. For this purpose nitric, 65.0 wt.%, and sulfuric, the volatiles as a fuel from waste. Also, this technology can 272
209 98.0 wt.%, acids were applied as received. Dry bentonite powder significantly reduce water and fuel content in the waste oil to limit 273
210 and acid solutions with concentrations of 0.5, 1.0, 1.5 and the ash content seriously. Along with settling, decanting and 274
211 2.0 mol l1 were separately prepared and heated up to 80 8C into filtering, distillation is used to treat waste oil in the most of 275
212 three-neck flask. The experimental setup consisted of a 1000 ml regeneration units. The dehydration of waste oil was performed in 276
213 flask equipped propeller mixer, condenser and thermometer. a simple batch distillation to eliminate water and light hydro- 277
214 Eighty grams of dry bentonite was added to 500 ml acid solution carbons. Water and gasoline fractions were separated at 200 8C. 278
215 and mixed thoroughly into the flask. The samples prepared as Distillation was carried out at 400 8C until no further distillate was 279
216 explained above, were activated during 15, 30, 45, 60, 90 and produced. The obtained oil was sent to the next steps that involve 280
217 180 min. The flask containing suspension was heated using the adsorption and filtration for further treatment. 281
218 laboratory water bath and the temperature was controlled by a
219 thermometer. The zero time was counted when the suspension Waste engine oil recovery 282
220 temperature reached to desired temperature. The temperature of
221 activation environment was continuously monitored to keep it in For regeneration of distillated oil and evaluation of activation 283
222 80  1 8C. After acidification, the mixture was filtrated and washed factors, the adsorption was performed by mixing different content 284
223 with de-ionized water in order to remove any excess acids and of natural and activated clays from 30.0 to 45.0 wt.%. Adsorption 285
224 released ions. Finally, the washed clay was dried in an oven at 60 8C was carried out to improve color and technical characteristics of 286
225 for 1 day and ground to obtain particles smaller than 75 mm. oil. Different content of adsorbents were added to 80 g distillated 287
226 The adsorption ratio of activated powders was measured by oil and mixed for 1 h by magnetic vibrating mixer. The suspensions 288
227 methylene blue, MB, adsorption as the following procedure were left at room temperature for 1 h to allow gravity for 289
228 [35,36]. MB powder (Merck 6045 Germany) was used in this sedimentation. The decolorized oils were separated from the 290
229 study. The chemical formula of MB is C16H18ClN3S with a adsorbent by a filter paper (Whatman, 40). 291
230 corresponding molecular weight of 319.86 g mol1. MB mole- The color evaluation was conducted using UV–Visible spec- 292
231 cules dissolve in aqueous solution as cationic dye, C16H18N3S+, troscopy (Model UV-1700 Pharma Spec, Shimadzu, Kyoto, Japan) 293
232 which is a large polar organic cation and is absorbed onto the by scanning the refined oils at the visible region. The structures of 294
233 negatively charged surfaces of clay minerals. Hence, the the resulting oils also were evaluated by Fourier transform infrared 295
234 adsorption ratio can be determined by the amount of MB spectroscopy (Model Unicam Mattson 1000, Philips, Almelo, The 296
235 absorbed onto natural and activated clays. The amount of MB Netherlands) in the wave number of 400–4000 cm1. 297
236 absorbed by given mass of clay depends on negative sites on the Specific gravity of regenerated oils was measured by a 298
237 clay particles. The MB solution was prepared by mixing 1.0 g of pycnometer. The kinematic viscosity of oils was determined by 299
238 dry powder with 200 ml of de-ionized water. The clay a capillary viscometer at 40 and 100 8C [37]. The temperature of 300
239 suspension was also obtained by mixing 2.0 g of oven-dry clay instrument was controlled by the paraffin bath at mentioned 301
240 with 120 ml of de-ionized water. The MB solution was added to values. 302
241 the clay suspension in 0.5 ml increments. After mixing suspen- The flash point is the lowest temperature in which the ignition 303
242 sion, 15–20 min for the each addition of MB, a small drop of it of produced vapor is observed. Fifty milliliters of regenerated oil 304
243 was removed and placed in Fisher brand filter paper P5. MB ions was placed into an open cup and the temperature was increased 305
244 coat the clay mineral surfaces and the end point is obtained slowly, near the flash point. At specified intervals, a flame was 306
245 when the unabsorbed MB forms a permanent light blue halo passed across the cup. This temperature is the flash point [38]. For 307
246 around the clay aggregate spot. The entire experimental the measurement of pour point, the oil was cooled at a constant 308
247 procedure was found to give satisfactory reproducible results. rate and examined at the specified intervals to observe the flow. 309

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310 It is the lowest temperature in which the movement of oil is 1.2

311 recorded [39]. Activated by H2SO4
312 For the measurement of ash content, the refined oil was
Activated by HNO3
313 contained in a ceramic cup and heated up to 775 8C in an electrical
314 kiln, allowed to burn until only ash and carbon remained. It was 1
315 cooled and weighed to calculate the ash percentage [40].

Adsorption ratio
316 Total acid number, TAN, is the weight of potassium hydroxide
317 required to neutralize the refined oil. The usual major components
318 of such materials are organic acids. TAN is an important factor for 0.8
319 lubricant engine oil quality for definition oxidation. Fifty milliliters
320 of ethanol was weighed into a baker in which a phenolphthalein
321 indicator was added and heated to 40 8C. The used alcohol was
0.6
322 neutralized with potassium hydroxide solution, 0.50 N. The
323 neutralized alcohol was added to 10.0 g oil and then stirred to
324 ensure complete extraction of acid by alcohol. Two drops of
325 phenolphthalein solution was added and the mixture was titrated 0.4
326 with potassium hydroxide solution, again. TAN can be calculated 0 0.5 1 1.5 2 2.5
327 by the following equation: -1
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi Acid concentration (mol.l )
2
NA V KOH b  b  4ac
TAN ¼ 56:1 (1) Fig. 1. The adsorption ratios of activated clays versus acid concentration.
W Oil 2a

329
328 where NA is the normality of KOH solution, VKOH the volume of KOH 1.1
330 solution used and WOil the weight of oil [41]. Activated by H2SO4: 1.00 mol.l-1
331 The alkaline base materials are added to engine oil for
1 Activated by HNO3: 1.00 mol.l-1
332 neutralizing the acidic products. The total base number, TBN, is
333 a factor for the replacement of oil after specific time. TBN
334 measurement involves titration of lubricant oil dissolved in a 0.9
Adsorption ratio

335 mixture of solvent such as chlorobenzene and glacial acetic acid

336 with a titrant such as perchloric acid in glacial acetic. Hundred 0.8
337 milliliters of refined oil was weighed into a beaker and 2.0 g
338 titration solvent was added. After mixing oil and solvent, the 0.7
339 mixture was titrated with perchloric acid in glacial acetic acid,
340 0.10 N. For visual determination, two drops of para-naphtholben-
0.6
341 Q6 zein indicator is added to the mixture before titration. The end
342 point of titration is identified if the orange color changes to green
343 or brown green. A blank titrant is prepared by adding 10 ml of 0.5
344 titration solvent into a beaker without any sample and then
345 titrated. TBN can be calculated as follows: 0.4
0 30 60 90 120 150 180 210
NT ðV T  V B Þ
TBN ¼ 56:1 (2) Residence time (min)
W Oil
Fig. 2. The adsorption ratios of activated clays versus residence time, acid
347
346 where NT is normality of the titrant, which is equal to 0.0641 in this
concentration: 1.00 mol l1.
348 research, VT the volume of titrant used for titration of refined oil
349 and VB the volume of titrant used for blank titration [41].

350 Results and discussion reduces to minimum value. The adsorption of MB rapidly falls 368
down initially and then remains constant between 30 and 60 min. 369
351 Natural and treated clays characterization Beyond 60 min, the adsorption ratio decreases slowly and there is 370
no significant reduction in the MB uptake. The maximum 371
352 The adsorption ratios of activated clays versus acid concentra- adsorption ratio was achieved during 15 min and it is independent 372
353 tion were plotted in Fig. 1. As the sulfuric acid concentration rises, on activation agent type. The adsorption of MB onto modified 373
354 the value of adsorption ratio decreases linearly up to a minimum adsorbent surface is favored when the clay is treated by nitric acid. 374
355 value. As the concentration of acid increases from 0.50 to Based on the above results, the activation time plays a vital role in 375
356 1.00 mol l1, the acid attacks the structure of clay minerals; this system. In general, an increase in the time leads to reduce in 376
357 therefore, the reduction in adsorption ratio is observed. This MB adsorption. 377
358 phenomenon shows that the concentration of acid is a very The chemical analysis of natural bentonite is reported in 378
359 important parameter in the acidification. The identical behavior in Table 1. The clay consists of silica and alumina. In particular, the 379
360 the nature of the plots is observed when activation is carried out in material shows the low Al2O3/SiO2 ratio, 0.18, while it is 380
361 the presence of nitric acid. The adsorption is highly dependent on characterized by comparable amount of CaO + MgO, 7.57 wt.%. 381
362 activation agent type, which affects the clay structure. This material is Ca-bentonite since the content of calcium is higher 382
363 The effect of residence time on the adsorption ratio was also than the amount of sodium. The used clay also displays the low 383
364 investigated in the range of 15–180 min as presented in Fig. 2. For proportion of alkali oxides, 1.06 wt.%. Also, the low content of iron 384
365 evaluation of residence time effect, the acid concentration kept oxide was found in raw materials. The noteworthy amounts of 385
366 constant at level of 1.00 mol l1. When the time is increased, the other elements are observed in bentonite. The effect of acid type on 386
367 adsorption ratio of clays treated by sulfuric acid non-linearly leaching process is also investigated by obtaining chemical 387

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Table 1
The chemical composition of natural and activated clays (wt.%).

Adsorbent SiO2 Al2O3 K2O Na2O CaO MgO Fe2O3 L.O.Ia

Natural bentonite 67.72 11.89 0.77 0.29 4.20 2.50 0.83 11.57
Activated clay by HNO3 70.95 12.53 0.38 0.19 0.89 1.68 0.84 12.38
Activated clay by H2SO4 67.21 11.69 0.55 0.24 2.59 1.60 0.61 15.33
a
Loss on ignition.

388 analyses of activated bentonite as reported in Table 1. The It is assumed that the chemical changes that take place in the 409
389 activation was performed by acid solutions in which the structure of clay minerals due to acid treatment lead to vacancies 410
390 concentration was 1.00 mol l1. Also, the residence time was in the crystal lattice. It is expected that the number of empty spaces 411
391 considered to be 30 min. The acid treatment modified the structure in the clay activated in the presence of nitric acid is higher than 412
392 of bentonite as indicated by the change in the chemical that in the clay activated by sulfuric acid. In order to provide charge 413
393 composition. The both acids showed significant effects on chemical equilibrium, the protons of acids are replaced with the exchange- 414
394 composition. Higher acid concentration enhances the removal of able cations, such as Ca2+, which are presented between the layers. 415
395 alkaline earth elements, but nitric acid exerts a major influence on However, the protons cannot fill all the empty spaces left by ions 416
396 Ca content. When the nitric acid solution is applied for activation, such as Mg2+ that occupy the octahedron positions; hence, the 417
397 the chemical composition is affected significantly. The application number of vacancy increases considerably. 418
398 of sulfuric acid in activation process did not promote the extraction The mineralogy of the natural bentonite and activated clays is 419
399 of Ca in comparison to that by nitric acid solution. It is expected shown in Fig. 3. The acid treatment was carried out by 420
400 that the exchangeable cations such as Ca2+ and Mg2+ are removed concentrated nitric and sulfuric acids, 1.00 mol l1, during 421
401 during the acid treatment. However, some parts of these elements 30 min. The XRD pattern of natural clay indicates the substantial 422
402 remain in the activated clays. The increase in SiO2 and Al2O3 amount of montmorillonite in the bulk material. The raw material 423
403 content, in the clay activated by nitric acid, is accompanied by predominantly consists of cristobalite as a major impurity, as well 424
404 decrease in content of CaO + MgO. H2SO4 is inefficient in removal as trace amounts of feldspar. The term cristobalite is used because 425
405 of Ca from clay mineral structure in comparison to HNO3. The iron the international diffraction data for the silica admixture shows 426
406 oxide content of clay activated by HNO3 is very low compared to that the sample is more indicative for cristobalite than the 427
407 that for natural clay. It is obvious that the amount of Mg in other silica phases. The activation by nitric and sulfuric acids 428
408 octahedral sheet decreases considerably in the presence of acids. was unsuccessful in removing cristobalite. The acid treatment 429

Fig. 3. The XRD patterns of natural bentonite and clays treated by concentrated nitric and sulfuric acid solutions.

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430 introduces some changes into the crystal structure of bentonite. Table 2
The physical properties of natural and activated bentonites.
431 The main reflection is observed in the region of 48 < 2u < 88. This
432 peak corresponds to diffraction angle of 5.968, in which the inter- Adsorbent Specific Pore Average
433 lamellar distance was found to be 8.7 Å. The intensity of surface volume pore
area (m2 g1) (cm3 g1) size (nm)
434 montmorillonite peak decreases due to acid treatment by H2SO4
435 and yields peak spacing, which was absent in the XRD pattern of Natural bentonite 31.8 0.093 11.7
436 clay activated by HNO3. After activation by sulfuric acid, the Activated clay by HNO3 81.6 0.230 11.3
Activated clay by H2SO4 76.9 0.220 11.5
437 position of mentioned peaks (0 0 1) is shifted. This implies changes
438 in the regular pattern of the montmorillonite along with partial
439 destruction compared to the original material. The decrease in the
440 interlayer region, 2.7 Å resulting from the acid treatment, can be clay is higher than untreated clay, the difference is approximately 473
441 attributed to the exchange of Ca2+ with H+. The increment in loss on 50 m2 g1. It returns to reactivity of acid with clay crystal in which 474
442 ignition, L.O.I in Table 1, is due to substitution of H+ in interlayer the surface area increases mainly in the edge area of crystals. The 475
443 spaces. It can also be observed that the characteristic peaks rises in specific surface area and volume are result of unoccupied 476
444 corresponding to gypsum appeared after acid activation by sulfuric octahedron spaces remaining from Mg2+ cations that leave the 477
445 acid, whereas feldspar is not destroyed, indicating that feldspar is layers of montmorillonite. As the activation progresses, the empty 478
446 resistant to acid attack. The XRD characterizations show that the spaces grow larger and micropores are transformed into meso- 479
447 structural properties of montmorillonite are not fundamentally pores, 12 nm. It is obvious that the average pore size approxi- 480
448 influenced by treatment with HNO3. mately remained constant but the number of nanopores is higher 481
449 The FTIR spectra of raw and activated clays were carried out in in the treated clays. This factor is the main reason, entailing 482
450 the range of 400–4000 cm1 to study the effects of acids on the clay considerable increase in empty spaces when HNO3 is used. 483
451 structure. The FTIR spectra of natural and activated bentonites are Therefore, the adsorption of MB is remarkably affected by acid 484
452 illustrated in Fig. 4. In the O–H stretching region, the natural clay type. The predominant MB retention mechanism is due to cation 485
453 shows that the two prominent bands at 3632 cm1 correspond to exchange [42]. The broken Mg–OH bonds of clay crystals results in 486
454 Al–OH and Mg–OH vibrations. The hydroxyl groups, lying between the increment of negative charge in the clay structure and the MB 487
455 the tetrahedral and octahedral sheets give the absorption around cations can easily adsorbed on clay surface, consequently. 488
456 3632 cm1. The wide band observed at 3454 cm1, assigned to the
457 Q7 high amount of water physically absorbed by the clays. The peak at Regenerated oils evaluation 489
458 wave number of 1640 cm1 is related to the bending vibration of
459 physically absorbed water. The infrared spectrum of the natural For the regenerated oils, the UV–Visible spectra were obtained 490
460 clay reveals the presence of SiO2. The band at 798 cm1 can be between 200 and 1200 nm. The comparison between the UV 491
461 ascribed to cristobalite. The spectrum shows intensive band at absorbance peaks is made to determine which oil was well refined. 492
462 1090 cm1 attributed to the hydrous Si–O stretching vibrations. Fig. 5 indicates the effect of adsorbent content on the colorant 493
463 The band at 626 cm1 is identified as a vibration in the octahedral behavior of refined oil. Different amounts of natural clay were 494
464 layers such as Al–O–Si and Mg–O–Si. The bands at 520 and added to distillated oil. The adsorption is highly dependent on 495
465 477 cm1 were assigned to Si–O–Al and Si–O–Si bending, adsorbent content which affects the UV absorbance. A peak at 496
466 respectively. There are no considerable changes in the FTIR spectra wavelength of 530 nm was observed in the spectrum of oil 497
467 of clays activated by nitric and sulfuric acids. regenerated by 30 wt.% natural clay. The maximum absorbance at 498
468 The physical properties of natural bentonite and activated clays wavelength of 510 nm is seen in the patterns of oils refined by 40.0 499
469 are presented in Table 2. The measured value indicates a very low and 45.0 wt.% bentonite. The peak intensity of oil recovered by 500
470 specific surface area and volume for untreated bentonite and these maximum content of bentonite is lower than the others. As shown 501
471 properties are improved when activation is carried out in the in Fig. 5, the oil color was not changed significantly and remains 502
472 presence of HNO3. Although the specific surface area of activated dark when the content of natural clay is less than 40.0 wt.%. The 503
blackness of oil could be due to the formation of small carbon 504

Fig. 4. The FTIR spectra of natural bentonite and clays treated by concentrated nitric
and sulfuric acid solutions. Fig. 5. The UV patterns of oils refined by different content of natural bentonite.

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505 particles during thermal cracking and oxidation. The oil may be the activation is carried out in the presence of sulfuric acid 525
506 contaminated with soot resulting from an incomplete combustion (Fig. 6(b)). 526
507 in motor. The presence of contaminants in used oil will be The effect of residence time on UV–Visible absorbance was also 527
508 discussed later. By contrast, the color of oil was effectively changed studied at the range of 15–120 min (Fig. 7). For evaluation of 528
509 when it was mixed with 45.0 wt.% clay. The selected bentonite residence time effect on UV absorbance, the activation environ- 529
510 shows a low reactivity with the contaminants because the ment concentration kept constant at level of 1.00 mol l1. When 530
511 distillated oil needs high amount of adsorbent for recovery. It is the activation time was increased, the UV absorbance was not 531
512 obvious that the base oil resulting from clay treatment is brighter changed remarkably. The removal of contamination by clays 532
513 and has a clear reddish color. activated in the presence of sulfuric acid is rapid in comparison to 533
514 The influence of acid concentration of activation environment that for clays treated by nitric acid. The significant variation in the 534
515 on UV absorbance of refined oils was investigated by obtaining the absorbance is not observed when activation time is less than 535
516 peak intensity at maximum wavelength, lmax. When the oil color 60 min. The sharp change occurs in UV absorbance beyond 60 min 536
517 changes from reddish to yellow, the maximum wavelength and there is no significant variation in the absorbance for oils 537
518 remains constant at approximately 510 nm. If the acid concentra- refined by clays activated above 90 min. The adsorption of 538
519 tion is increased from 0.50 to 1.00 mol l1, the absorbance contaminations by activated clay is also affected by acid type. 539
520 decreases sharply (Fig. 6(a)). These data indicate that the acid The clay modified by sulfuric acid favors for recovery process, 540
521 concentration plays an important role in the adsorption capacity. because the UV absorbance of oils refined by clays activated in the 541
522 The UV absorbance of regenerated oil by bentonite treated in the presence of nitric acid is always higher than that for oils recovered 542
523 presence of sulfuric acid, 1.00 mol l1, is comparable with other by clays activated in the presence of sulfuric acid at the same 543
524 data. The maximum removal of contaminants was observed when condition. In conclusion, not only the high specific surface area, but 544
also interlayer spacing of montmorillonite has substantial effect on 545
regeneration of waste oil. The relation between MB adsorption 546
level and removal of contaminations were not observed in the 547
regeneration of waste oil. 548
The adsorbent content is the most important factor, affecting 549
the regeneration process. In order to study the influence of 550
activated clay content on adsorption, the UV absorbance is plotted 551
versus adsorbent content in Fig. 8. It is clear that the adsorption is 552
highly dependent on adsorbent content. Maximum removal of 553
contaminations is carried out by clay activated by sulfuric. When 554
the amount of clays is increased, the absorbance decreases linearly. 555
Conversely, a lower adsorption is observed by natural clay. The 556
uptake of contaminations by clay activated in the presence of 557
sulfuric acid increases considerably, which indicates 17 wt.% 558
reduction in the adsorbent content to achieve the same absor- 559
bance, approximately. 560
In order to determine the chemical composition of regenerated 561
oils, FTIR technique was used as shown in Fig. 9. The same 562
information, regarding to the most important bands, were 563
observed in the spectra of examined oils. By recording the oil 564
spectrum after recovery, it is possible to understand the changes 565
occurring in oil composition. The refined oils are a mixture of 566
hydrocarbons. The bands related to C–H vibrations appear in the 567
range 2737 and 2860–2961 cm1. The intense band occurred at 568
wave number of 1465 cm1 shows C–H plain bending vibration. 569

3
Activated by H2SO4
2.5 Activated by HNO3

2
Absorbance

1.5

0.5

0
0 20 40 60 80 100 120 140
Fig. 6. (a) The UV absorbance of oil versus acid concentration. (b) The UV patterns of Activation time (min)
oils refined by clays treated by concentrated nitric and sulfuric acid solutions,
1.00 mol l1. Fig. 7. The UV absorbance of oil versus residence time.

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8 S. Salem et al. / Journal of Industrial and Engineering Chemistry xxx (2014) xxx–xxx

3 higher aromatic content in gasoline. The absence of aromatic 591

Raw bentonite material peaks at 570–800 cm1 show that the oils are well 592
distillated. 593
2.5 Activated by Water is a very strong FTIR absorber and is very easy to detect. It 594
H2SO4 also appears in the region that few bands appear in infrared 595
Activated by spectrum of oil. Water is detected as a broad feature, centered on 596
2 HNO3 3400 cm1. Glycol has a characteristic peak around 880 cm1 as 597
well as peaks at 1040, 1080 and 3400 cm1. The other peaks in the 598
Absorbance

1.5 spectrum related to glycol are used to confirm its presence. The 599
peak at 880 cm1 is used to identify glycol because it is not subject 600
to interferences with the other bands. The related peaks show the 601
1 absence of glycol and limited amount of water. The distillation at 602
400 8C removed the water and glycol satisfactorily. 603
Sulfur by-products such as SO2 and SO3 are the result of sulfur 604
0.5 compound oxidation in fuel during combustion as well as 605
oxidation of additives. These compounds increase the production 606
of varnish and sludge in the degraded oil. They also react with the 607
0
25 30 35 40 45 50 water formed during combustion to produce powerful inorganic 608
Adsorbent content (wt.%) acids such as sulfuric acid. Sulfates can be identified by monitoring 609
their characteristic infrared bands, found at wave number of 610
Fig. 8. The UV absorbance of oil versus adsorbent content. 1150 cm1. The vibration in this wave number is not detected. 611
When organic compounds are exposed to high temperatures 612
and pressures in the presence of oxygen, the nitrogen oxides are 613
formed. These products cause the increase in acidity, varnish and 614
sludge due to the formation of higher molecular weight 615
compounds. These are generally in the form of nitrogen oxides 616
such as NO, NO2 and N2O4. In addition, the nitration products are 617
the major reason for build-up of varnish. They have a characteristic 618
peak between 1600 and 1650 cm1. The infrared spectra show the 619
absence of nitration products in refined oils. 620
When the organic compounds of engine oil are exposed to the 621
high temperatures and pressures, these materials partially react 622
with the oxygen. There is a wide variety of by-products produced 623
during the combustion process such as carboxylic acids. Some of 624
these compounds are dissolved or dispersed in the oil. Carboxylic 625
acids contribute to increase the acidity of oil. The chemical effect of 626
oxidation is corrosion and the increment in viscosity also occurs 627
simultaneously. The oxidation can be identified by FTIR. If 628
oxidation is carried out in the oil, a general response for carbonyl 629
(C55O) is observed between 1670 and 1800 cm1 and around 630
2360 cm1. In this region, infrared energy is absorbed due to the 631
carbon–oxygen bonds in the waste oil. The above vibrations are not 632
Fig. 9. The FTIR spectra of oils regenerated by natural bentonite and clays treated by observed in the oil spectra refined by activated bentonite but a 633
concentrated nitric and sulfuric acid solutions. negligible amount of carboxylic acid was found in oil recovered by 634
natural bentonite. 635
570 Generally, hydrocarbons containing methyl, CH3, groups indicate When fuel and air mixture is burned, soot particles are formed. 636
571 vibration at 1370–1380 cm1. Also, CH2 rocking is observed at Soot build-up is a problem, causing the change of oil viscosity. The 637
572 wave number of 721 cm1. The peaks in wave number of 816, 970, FTIR analysis of soot is different than the methods used for 638
573 1310 and 1611 cm1 are related to C5 5C bond in aromatic ring. The identification of other contaminants, because specific infrared 639
574 FTIR spectra display limited amount of aromatic components in the bands are lack for soot. The soot particles cause a general scattering 640
575 regenerated oils. of the infrared radiation, which is more severe at higher wave 641
576 The most common contaminations found in the degraded oil numbers. Soot is identified by taking to account the intensity at 642
577 are fuel, glycol pollutions, oxidation, nitrating and sulfating wave number of 2000 cm1. The absence of soot in the refined oils 643
578 components, soot and water accumulation [43]. Fuel contamina- is confirmed by FTIR spectra. 644
579 tions coming from combustion chamber or line leakage have the The technical characteristics of oils regenerated by industrial 645
580 lower boiling point. The condition in engine causes the change of raw material and treated clays are reported in Table 3. The density 646
581 fuel composition, due to incomplete combustion and distillation of of oils refined by natural clay is higher than that for oil regenerated 647
582 lighter fractions. Since the lubricating base oil is derived from by treated bentonites. The kinematic viscosity at 40 8C rises when 648
583 crude oil distillation cuts, they are very similar in chemical regeneration is carried out by activated clays, indicating the better 649
584 composition and physical nature. The FTIR technique is a more fast removal of contaminants from oil. Furthermore, regeneration of 650
585 and simple way for identification fuel contaminations. The main waste oil by activated clay cannot significantly change the 651
586 difference between the fuel and base oil is the boiling range and the viscosity at 100 8C. It is very interesting that the flash point of 652
587 percentage of aromatic materials. Fuel has a lower boiling range oil recovered by raw materials is higher than that for oils 653
588 and significantly higher amount of aromatic compositions. The regenerated by clays treated in the presence of nitric and sulfuric 654
589 vibrations at the range of 570–800 cm1 are used for this purpose. acids. Also, the pour point of studied oils remained constant, 655
590 Gasoline contamination detection is very easy because of the approximately. The reported ash content is favorable that satisfies 656

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S. Salem et al. / Journal of Industrial and Engineering Chemistry xxx (2014) xxx–xxx 9

Table 3 4 A clear relationship between the MB adsorption and UV–Visible 711

710
The technical characteristics of oils regenerated by natural and activated clays.
absorbance was not observed. Although the higher specific 712
Property Natural Activated Activated surface area is necessary for removal of contaminants from used 713
bentonite by H2SO4 by HNO3 lubricant oil, the interlayer spacing should be considered in 714
Density (g cm3) at 27.5 8C 0.923 0.908 0.891 evaluation of activated bentonite. 715
Kinematic viscosity at 40 8C (cSt) 38.9 46.5 46.8
Kinematic viscosity at 100 8C (cSt) 7.2 7.4 7.4
Flash point (8C) 198 170 183
Pour point (8C) 1 2 1 Acknowledgment 716
Ash content (wt.%) Nil Nil 0.014
Total acid number (mg KOH/g oil) 0.1 Nil Nil The distillation of waste engine oil was carried out by Shahab 717
Total base number (mg HCl/g oil) 0.1 Nil 0.6 Gatran Company. The authors would like to thank this company for 718
providing the distillated oil in the industrial scale. 719

657 the standard limitation. The results also show that the total acid References 720
658 number of oils regenerated by modified clays is negligible while
659 the TAN of oil refined by natural clay is higher than the standard [1] A.R. Landsdown, Lubrication and Lubricant Selection: A Practical Guide, third ed., 721
John Wiley & Sons, 2003. 722
660 value, <0.03. The reduction in the TAN is due to adsorption of [2] W. Holweger, in: J. Gegner (Ed.), Tribology—Fundamentals and Advancements, 723
661 contaminants. The lower total acid number shows the greater InTech, New York, 2013, pp. 3–52. 724
662 stability of oil. The acidity of oil may be due to the presence of [3] S.O. Ogbeide, J. Eng. Sci. Technol. Rev. 3 (1) (2010) 32. 725
[4] M. El-Fadel, R. Khoury, Resour. Conserv. Recycl. 33 (2) (2001) 75. 726
663 carbonyl components. These compounds are present in low [5] R.A. Beg, M.R.I. Sarker, M.R. Pervez, J. Mech. Mechatron. Eng. 10 (2) (2010) 1–5. 727
664 quantity after recovery. The total base number of regenerated [6] S.S. Lam, A.D. Russell, C.L. Lee, S.K. Lam, H.A. Chase, J. Hydrogen Energy 37 (2012) 728
665 oil by clay modified in the presence of sulfuric acid is negligible. 5011. 729
[7] M.J. Diphare, E. Muzend, T.J. Pilusa, M. Mollagee, in: Proceedings of 2nd Interna- 730
666 The color of the oils refined by natural material and modified clay tional Conference on Environment, Agriculture and Food Sciences, August 25–26, 731
667 in the presence of nitric acid was reddish while the color of the 2013; Kuala Lumpur, Malaysia, 2013 (106–109). 732
668 regenerated oil by clay modified in the presence of sulfuric acid [8] J. Rincon, P. Canizares, M.T. Garca, J. Supercrit. Fluids 39 (2007) 315. 733
[9] S.S. Lam, A.D. Russell, H.A. Chase, Energy 35 (2010) 2985. 734
669 was yellow. The clay activated by sulfuric acid was observed to be a [10] S.S. Lam, A.D. Russell, C.L. Lee, H.A. Chase, Fuel 92 (2012) 327. 735
670 better adsorbent than the other studied cases. The improvement in [11] H. Bridjanian, M. Sattarin, Petrol. Coal 48 (1) (2006) 40. 736
671 oil color and characteristics can be achieved by hydro-treating [12] M.M. Rahman, T.A. Siddiquee, S. Samdani, K.B. Kabir, Chem. Eng. Res. Bull. 12 737
672 process due to decrease in the content of unsaturated components (2008) 24. 738
[13] Y.L. Hsu, C.H. Lee, V.B. Kreng, Wseas Trans. Environ. Dev. 5 (3) (2009) 295. 739
673 [11]. Because the additives were degraded during the serves or [14] E.A. Emam, A.M. Shoaib, Petrol. Coal 55 (3) (2013) 179. 740
674 eliminated from the oil by distillation and adsorption, the viscosity, [15] M. Shakirullah, I. Ahmad, M. Saeed, M.A. Khan, H. Rehman, M. Ishaq, A.A. Shah, J. 741
675 flash point, pour point and TBN of oil can be improved by mixing Chin. Chem. Soc. 53 (2006) 335. 742
[16] N.O. Elbashir, S.M. Al-Zahrani, M.I. Abdul Mutalib, A.E. Abasaeed, Chem. Eng. 743
676 the suitable additives to satisfy the standard requirements. Process. 41 (2002) 765. 744
[17] S.M. Al-Zahrani, M.D. Putra, J. Ind. Eng. Chem. 19 (2013) 536. 745
[18] V. Katiyar, S. Husain, J. Chem. Sci. 8 (3) (2010) 1999. 746
[19] A. Kamal, F. Khan, Oil Gas Sci. Technol. Rev. IFP 64 (2) (2009) 191. 747
677 Conclusions [20] R. Abro, X. Chen, K. Harijan, Z.A. Dhakan, M. Ammar, Chem. Eng. J. (2013) 1. 748
[21] R.R. Mohammed, I.A.R. Ibrahim, A.H. Taha, G. McKay, Chem. Eng. J. 220 (2013) 343. 749
678 The present study demonstrated the feasibility of Iranian [22] N.M. Abdel-Jabbar, E.A.H. Al Zubaidy, M. Mehrvar, Int. J. Chem. Biol. Eng. 3 (2) 750
(2010) 70. 751
679 activated bentonite, from Soltaniyeh in Zanjan province, for [23] J.L. Assuncao Filho, L.G.M. Moura, A.C.S. Ramos, Braz. J. Chem. Eng 27 (4) (2010) 752
680 regeneration of used lubricant oil by clay treatment process. The 687. 753
681 acidification of natural clay was carried out by concentrated HNO3 [24] J.D. Udonne, J. Petrl. Gas Eng. 2 (2) (2001) 12. 754
[25] E. Al Zubaidy, Int. J. Environ. Pollut. Remediat. 1 (1) (2012) 38–43. 755
682 and H2SO4 solutions and the conclusions can be summarized as [26] I. Hamawand, T. Yusaf, S. Rafat, Energies 6 (2013) 1023. 756
683 follows: [27] L. Nasrat, M. Abdelwahab, G. Ismail, Engineering 3 (2011) 588. 757
[28] L. Nasrat, M.S. Hassan, World Acad. Sci. Eng. Technol. 68 (2012) 1089. 758
[29] R.E. Grim, Clay Mineralogy International Series in the Earth and Planetary 759
685
686 1 The acid treatment results in re-organization of the pore Sciences, second ed., McGraw-Hill, New York, 1968. 760
687 structure by leaching Mg from octahedral sheet, creating [30] R.E. Grim, Applied Clay Mineralogy, McGraw-Hill, New York, 1962. 761
688 vacancies. The concentrated nitric acid, 1.00 mol l1, is efficient [31] E.G. Kirali, O. Lacin, J. Food Eng. 75 (2006) 137. 762
689 in the removal of Mg from the montmorillonite structure but [32] R. Francisco, D. Valenzuela, D.E.S. Persio, Quim. Nova 24 (3) (2001) 345. 763
[33] H. Babaki, A. Salem, A. Jafarizad, Mater. Chem. Phys. 108 (2008) 263. 764
690 sulfuric acid affects the interlayer spacing by substitution of [34] M. Onal, Y. Sarikaya, T. Alemdaroglu, Turk. J. Chem. 26 (2002) 409. 765
691 hydrogen ions. The nitrogen adsorption isotherms indicated that [35] E. Cokca, Turk. J. Eng. Environ. Sci. 26 (2002) 521. 766
692 the average pore size, 12 nm, is independent on acid type. The [36] A. Salem, M. Saghapour, Prog. Color Colorants Coat. 6 (2013) 97. 767
[37] ASTM D 445-04, Standard Test Method for Kinematic Viscosity of Transparent and 768
693 increase in number of nano-pores due to treatment by nitric acid Opaque Liquids and the Calculation of Dynamic Viscosity, in: Annual Book of 769
694 is more prominent in comparison to that by sulfuric acid. Standards, American Society for Testing and Materials, West Conshohocken, PA, 770
695
696 2 The methylene blue adsorption tests confirm that the structural 2004. 771
[38] ASTM D 92-02b, Standard Test Method for Flash and Fire Points by Cleveland 772
697 changes in clay due to acidification. The MB uptake by treated Open Cup Tester, in: Annual Book of Standards, American Society for Testing and 773
698 clays is directly related to specific surface area. Materials, West Conshohocken, PA, 2002. 774
699
700 3 The uptake of oil contaminants on the treated clays is affected by [39] ASTM D 97-04, Standard Test Method for Pour Point of Petroleum Products, in: 775
Annual Book of Standards, American Society for Testing and Materials, West 776
701 acid treatment condition. It continuously increases with acid Conshohocken, PA, 2004. 777
702 concentration until the clay destruction is observed. The acid [40] ASTM D 482-03, Standard Test Method for Ash from Petroleum Products, in: 778
703 type and concentration are two important factors that influence Annual Book of Standards, American Society for Testing and Materials, West 779
704 the oil regeneration process. The activation of bentonite by Conshohocken, PA, 2003. 780
[41] ASTM D 974-02, Standard Test Method for Acid and Base Number by Color 781
705 sulfuric acid, 1.00 mol l1, yields an adsorbent material that is Indicator Titration, in: Annual Book of Standards, American Society for Testing 782
706 efficient in removal of color from waste oil and is better than the and Materials, West Conshohocken, PA, 2002. 783
707 natural one. In spite, the decolorizing power of clay treated by [42] M.G. Neumann, F. Gessner, C.C. Schmitt, R. Sartori, J. Coll. Interface Sci. 255 (2002) 784
254. 785
708 nitric acid at the same condition was shown to be inefficient for [43] F.R. Van de Voort, J. Sedman, R.A. Cocciardi, D. Pinchuk, Tribol. Trans. 49 (2006) 786
709 Q8 the recovery of used lubricant oil. 410. 787

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