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Fuel Processing Technology 88 (2007) 913 920 www.elsevier.

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Separation of different paraffin wax grades using two comparative deoiling techniques
Magdy T. Zaky , Nermen H. Mohamed, Amal S. Farag
Petroleum Refining Division, Egyptian Petroleum Research Institute (EPRI), Nasr City, P. O. Box 11727, Cairo, Egypt Received 26 November 2006; received in revised form 26 April 2007; accepted 30 April 2007

Abstract One stage fractional crystallization and solvent percolation techniques have been used to separate different grades of paraffin waxes; with different characteristics; from El-Ameria light, middle and heavy slack waxes. The two deoiling techniques were performed using ethyl acetate and butyl acetate solvents at ambient temperature of 20 C, at different dilution solvent ratios (S/F by weight) ranging from 2:1 to 8:1 and constant washing solvent ratio of 2:1 for the first technique and at different percolation solvent ratios ranging from 4:1 to 14:1 for the second one. The resulting data revealed that fractional crystallization technique is more suitable for deoiling the heavy slack wax using butyl acetate solvent than the percolation technique. While, percolation technology is a preferable technique using ethyl acetate or butyl acetate solvent for separation of paraffin waxes from light and middle slack waxes. 2007 Elsevier B.V. All rights reserved.
Keywords: Paraffin waxes; Fractional crystallization; Solvent percolation; Deoiling techniques; Slack waxes

1. Introduction Generally, paraffin waxes are derived from low-boiling wax distillate fractions (light and middle ones). They consist mainly of n-paraffins ranging from C16 to C30 and possibly higher. Varying proportions of slightly branched-chain paraffins (C18C36) and naphthenes are present. Fully, semi- and scale refined paraffin waxes are produced from slack waxes. Slack waxes separated from lubricating oil feedstocks by dewaxing operation, usually contain from 2 to 45 wt.% oil. Low oil content paraffin waxes with a specific melting point and needle penetration are produced by selective removal of the oil and low melting waxes from the slack waxes. This process is called deoiling or wax fractionation. The commercial wax fractionation processes are the wax sweating, the re-crystallization, the warm-up and the spray deoiling ones [1,2]. The most predominant process is the wax re-crystallization which was developed as a replacement for the wax sweating
Corresponding author. Tel.: +202 2745902; fax: +202 2747433. E-mail address: magdytadrous@hotmail.com (M.T. Zaky). 0378-3820/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.fuproc.2007.04.011

process. It is sometimes called wax fractional crystallization process and can be used to fractionate or deoil all types of waxes. The wax cake from the primary or the secondary dewaxing filters is heated until the wax is totally dissolved in the solvent. Additional warm solvent is blended with the wax cake solution. The mixture is cooled in double pipe scraped surface equipment to a predetermined temperature to crystallize the desired wax fractions. The mixture is filtered through a rotary vacuum filter and the wax cake receives a final wash. The filtration temperature of the wax in the third stage is conducted at a higher temperature than that used in the first or second dewaxing filtrations and the temperature used is selected to adjust wax melting point and penetration. This process can be operated in series with the solvent dewaxing unit of similar design, which uses double or incremental dilution and single or two-stage filtration [2]. The characteristics of an ideal dewaxing or deoiling solvent include the following: low solvent power of wax, high solvent power for oil, low freeze point, low viscosity, low in cost, nontoxic and have chemical and thermal stability [2]. In our previous study, n-hexane, dioxane, ethyl acetate and butyl acetate solvents were compared with methyl isobutyl

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M.T. Zaky et al. / Fuel Processing Technology 88 (2007) 913920 Table 2 Effect of dilution solvent ratio on the physical characteristics, type and molecular type composition of isolated waxes by one stage fractional crystallization of light slack wax using butyl acetate solvent at fractionating temperature of 20 C and S/F for washing of 2:1 Characteristics Light slack wax Waxes isolated at different dilution solvent to feed ratios (S/F) by using Butyl acetate 2:1 (L4) 4:1(L5) 6:1 (L6) Congealing point, C Kinematic viscosity at 98.9 C, mm2 s 1 Refractive index at 98.9 C Mean molecular weight Oil content, wt.% Needle penetration at 25 C Color (ASTM-D 1500) Refractive index by TAPPI-ASTM equation Ultraviolet absorbance at 290 nm Type of wax 48 3.04 1.4224 384 5.32 43 1.0 54 3.12 1.4179 406 0.33 22 0.0 1.4245 55.5 3.18 1.4193 414 0.20 19 0.0 1.4250 56.5 3.30 1.4199 421 0.06 17 0.0 1.4254

ketone (MIBK) solvent and methyl ethyl ketone (MEK), benzene (B) and toluene (T) (60:20:20 by weight respectively) solvent mixture; the conventional solvents generally used in refineries as dewaxing and deoiling solvents. The study indicated that, the most suitable solvents for separating paraffin waxes; with the standard specifications; from light, middle and heavy slack waxes are MIBK, ethyl and butyl acetates and the mixture of MEK, B & T. Moreover, butyl acetate and MIBK solvents and MEK, B & T solvent mixture can give paraffin waxes having nearly the same congealing points, needle penetrations and mean molecular weights range. However from the economical point of view, ethyl acetate and butyl acetate solvents are the most popular fractionating solvents due to their lower prices than MIBK solvent and their advantages of saving energy in the solvent distillation step over the solvent mixture of MEK, B &T [3]. Other authors carried out a study deals with the application of solvent percolation technique to separate oil from commercial microcrystalline wax flakes produced from tank bottom sludges. Wax deoiling has been accomplished by percolating industrial hexane through a packed bed of the wax flakes at ambient temperature and removing the solvent from the wax and oil phases to get hard wax and foot oil respectively. In this technology, mechanical mixing and filtration operation have been substituted with percolation of solvent through wax flakes, thereby eliminating mixed phase in the process and the need of expensive scraped surface crystallizers, rotarydrum filters and refrigeration equipment as required in conventional solvent deoiling [4].

0.057 0.056 0.052 Macro-crystalline

Thus, the present study deals with the differentiation between the fractional crystallization and solvent percolation techniques using ethyl acetate and butyl acetate solvents by variation the solvent feed ratios, for separation of various grades of paraffin waxes of different specifications from light, middle and heavy slack waxes.
2. Experimental

Table 1 Effect of dilution solvent ratio on the physical characteristics, type and molecular type composition of isolated waxes by one stage fractional crystallization of light slack wax using ethyl acetate solvent at fractionating temperature of 20 C and S/F for washing of 2:1 Characteristics Light slack wax Waxes isolated at different dilution solvent to feed ratios (S/F) by using Ethyl acetate 4:1 (L1) 6:1 (L2) 8:1 (L3) Congealing point, C Kinematic viscosity at 98.9 C, mm2 s 1 Refractive index at 98.9 C Mean molecular weight Oil content, wt.% Needle penetration at 25 C Color (ASTM-D 1500) Refractive index by TAPPI-ASTM equation Ultraviolet absorbance at 290 nm Molecular type composition Total saturates, wt.% n-paraffins content, wt.% Iso- and cyclo-paraffins content, wt.% Iso- and cyclo-paraffins/n-paraffins ratio Total aromatics, wt.% Mono-aromatics, wt.% Degree of branching (% CH3 content) Type of wax 48 3.04 1.4224 384 5.32 43 1.0 54 3.06 1.4189 400 0.49 24 0.5 1.4245 0.420 54.5 3.16 1.4191 406 0.29 19 0.0 1.4247 0.058 55 3.18 1.4193 408 0.08 14 0.0 1.4249 0.053

2.1. Materials
Three appropriate crude waxes; light, middle and heavy slack waxes; from El-Ameria Refining Company with different characteristics are used in this study for isolation of different grades of paraffin waxes. Ethyl and butyl acetate solvents are used for separation of paraffin waxes by both fractional crystallization and solvent percolation techniques.

2.2. Isolation of paraffin waxes


The three slack waxes were subjected practically to one stage fractional crystallization and solvent percolation techniques using ethyl and butyl acetate solvents at ambient temperature of 20 C and at different solvent feed ratios (S/F, by weight) ranging from 2:1 to 8:1 at fixed washing solvent ratio of 2:1 for the former technique and from 4:1 to 14:1 for the latter technique to produce different grades of paraffin waxes. 2.2.1. Fractional crystallization technique A known weight of slack wax was dissolved in the corresponding amount of solvent or solvent mixture in a beaker and heated till the mixture becomes homogenous. Then the mixture was cooled gradually at room temperature. The beaker and the buchner funnel were transferred to a controlled temperature unit and gradually cooled to the desired temperature. The beaker contents were transferred to the funnel and filtered through a Whatman filter paper No. 43 by using gentle suction. The wax cake was washed with additional solvent at the same temperature and added at small increments. Solvents were removed from the wax cake by distillation. 2.2.2. Solvent percolation technique A known weight of slack wax flakes was random packed in a jacketed glass column (diameter 3 cm, length 130 cm). A certain quantity of solvent was percolated under gravity over the packed bed of wax flakes from the top,

97.63 74.71 22.92 0.31 2.37 2.37 12.52

100 88.32 11.68 0.13 0.00 0.00 8.96 Macro-crystalline

100 89.90 10.10 0.11 0.00 0.00 8.30

M.T. Zaky et al. / Fuel Processing Technology 88 (2007) 913920 Table 3 Effect of percolation solvent ratio on the physical characteristics and type of isolated waxes by solvent percolation of light slack wax using ethyl acetate solvent at percolating temperature of 20 C Characteristics Light slack wax Waxes isolated at different percolation solvent to feed ratios (S/F) by using Ethyl acetate 6:1 (PL1) Congealing point, C Kinematic viscosity at 98.9 C, mm2 s 1 Refractive index at 98.9 C Mean molecular weight Oil content, wt.% Needle penetration at 25 C Color (ASTM-D 1500) Refractive index by TAPPI-ASTM equation Ultraviolet absorbance at 290 nm Type of wax 48 3.04 52.5 3.05 8:1 (PL2) 53 3.07 10:1 (PL3) 53.5 3.09 12:1 (PL4) 54 3.12 14:1 (PL5) 54 3.12

915

1.4224 1.4181 1.4183 1.4187 1.4196 1.4196 384 5.32 43 1.0 393 1.58 35 397 1.31 32 400 0.81 27 406 0.31 21 406 0.30 21

0.5 0.5 0.5 0.0 0.0 1.4240 1.4242 1.4243 1.4245 1.4245 0.04 0.04

Macro-crystalline

light, middle and heavy slack waxes by using ethyl and butyl acetate solvents at ambient temperature of 20 C. Data are represented in Tables 111. The wax yield decreases with increasing of dilution or percolation solvent ratios (Fig. 1), with the improvement of wax quality in terms of increasing the congealing point and mean molecular weight and lowering the needle penetration as a result of the decrease of oil content for the separated waxes. It can be noticed also that, the improvement in the wax quality is more pronounced with lower wax yield by using butyl acetate solvent than those obtained by ethyl acetate solvent for both techniques. This may be due to the higher solvent power of butyl acetate towards the oil inherent to such waxes (Tables 111). It is interest to note that the decrease in the oil content is accompanied with an increase in the viscosities and refractive indices of the waxes separated from light and middle slack waxes by increasing the dilution or percolation solvent ratios (Tables 18) while for the heavy slack wax, the decrease in the oil content is accompanied with the decrease in the viscosities and refractive indices of the separated waxes (Tables 911). This may be attributed to the type of the entrained oil which is mainly iso-paraffins having lower refractive indices and viscosities in the former case and aromatic constituents for the
Table 4 Effect of percolation solvent ratio on the physical characteristics, type and molecular type composition of isolated waxes by solvent percolation of light slack wax using butyl acetate solvent at percolating temperature of 20 C Characteristics Light slack wax Waxes isolated at different percolation solvent to feed ratios (S/F) by using Butyl acetate 4:1 (PL6) Congealing point, C Kinematic viscosity at 98.9 C, mm2 s 1 Refractive index at 98.9 C Mean molecular weight Oil content, wt.% Needle penetration at 25 C Color (ASTM-D 1500) Refractive index by TAPPI-ASTM equation Ultraviolet absorbance at 290 nm Molecular type composition Total saturates, wt.% n-paraffins content, wt.% Iso- and cycloparaffins content, wt.% Iso- and cyclo-paraffins/ n-paraffins ratio Total aromatics, wt.% Mono-aromatics, wt.% Degree of branching (% CH3 content) Type of wax 48 3.04 52.5 3.07 6:1 (PL7) 53.5 3.10 8:1 (PL8) 54 3.15 10:1 (PL9) 57.5 3.25 12:1 (PL10) 58 3.38

maintaining the temperature of the column at 20 C. After the percolation run, wax and oil solution phases were made free from the solvent by distillation to get hard wax and soft wax, respectively.

2.3. Methods of analysis


The three slack waxes and the isolated paraffin waxes were physically characterized according to American Society for Testing and Materials (ASTM) standard methods [5]. The type of the isolated paraffin waxes was specified according to Technical Association of the Pulp and Paper Industry (TAPPI) ASTM equation [6,7]. The aromatic contents of the slack waxes and the isolated paraffin waxes were determined using liquid - solid column chromatography technique [8]. n-paraffin contents were determined for the slack waxes and the isolated paraffin waxes using GC technique. The GC apparatus used was model 6890 plus Aglient, equipped with a hydrogen flame ionization detector and fused silica capillary column (30 m 0.25 mm i.d.), packed with poly (dimethyl siloxane) HP-1 (non-polar packing) of 0.5 m film thickness. The peak area of each resolved component (consisting of either n- and iso-paraffin) is determined individually. However, the unresolved complex mixtures (humps); composed of non n-paraffins presumably mainly cyclo-paraffins and aromatics with long side chains; were determined only as a total. The degree of branching (%CH3 content) of the slack waxes and the isolated paraffin waxes was determined using proton nuclear magnetic resonance (Varian Mercury H-NMR spectrometer-Danemark) at 300 MHz in deutrated chloroform [9]. Ultraviolet absorbance for the fully refined paraffin waxes was determined at 290 nm by using UV-Visible Spectrophotometer.

1.4224 1.4189 1.4199 1.4204 1.4213 1.4218 384 5.32 43 1.0 397 0.71 26 400 0.45 22 412 0.31 20 432 0.02 16 438 0.02 15

0.5 0.0 0.0 0.0 0.0 1.4240 14243 1.4245 1.4257 1.4259 0.039 0.025 0.022 0.019

97.63 74.71 22.92 0.31 2.37 2.37 12.52

3. Results and discussion 3.1. Fractional crystallization and solvent percolation of crude waxes 3.1.1. Effect of dilution and percolation solvent ratios The dilution and the amount of solvent used in fractional crystallization and percolation respectively, have an obvious effect upon the yield and quality of the waxes isolated from

100 80.01 19.99 0.25 0.00 0.00 9.52

100 89.83 10.17 0.11 0.00 0.00 8.80

Macro-crystalline

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M.T. Zaky et al. / Fuel Processing Technology 88 (2007) 913920

Table 5 Effect of dilution solvent ratio on the physical characteristics, type and molecular type composition of isolated waxes by one stage fractional crystallization of middle slack wax using ethyl acetate solvent at fractionating temperature of 20 C and S/F for washing of 2:1 Characteristics Middle Waxes isolated at different Slack dilution solvent to feed ratios Wax (S/F) by using Ethyl acetate 2:1 (M1) Congealing point, C Kinematic viscosity at 98.9 C, mm2 s 1 Refractive index at 98.9 C Mean molecular weight Oil content, wt.% Needle penetration at 25 C Color (ASTM-D 1500) Refractive index by TAPPI-ASTM equation Ultraviolet absorbance at 290 nm Molecular type composition Total saturates, wt.% n-paraffins content, wt.% Iso- and cyclo-paraffins content, wt.% Iso- and cyclo-paraffins/ n-paraffins ratio Total aromatics, wt.% Mono-aromatics, wt.% Degree of branching (% CH3 content) Type of wax 59 4.30 1.4270 446 6.23 40 1.5 61.5 4.10 1.4229 449 1.39 23 1.0 1.4271 4:1 (M2) 62.5 4.15 1.4234 455 1.14 19 1.0 1.4275 6:1 (M3) 63.5 4.23 1.4243 463 0.09 16 0.5 1.4278 0.283

96.97 62.89 34.08 0.54 3.03 3.03 10.78

98.82 64.02 34.80 0.54 1.18 1.18 9.65 Macro-crystalline

99.01 65.93 33.08 0.50 0.99 0.99 9.54

100 69.50 30.50 0.44 0.00 0.00 8.56

and cyclo-paraffins and mono-aromatic constituents of lower melting points and mean molecular weights decrease in the paraffin waxes isolated from the three slack waxes. But, the solvent percolation technique needs higher quantity of solvent necessary for deoiling to obtain paraffin wax with nearly the same specifications as those obtained by fractional crystallization. Thus, to obtain paraffin wax with penetration value of nearly 19 by percolation and fractional crystallization techniques, the quantities of butyl acetate required per unit slack wax are 8:1 & 6:1 respectively (compare PL8 in Table 4 with L5 in Table 2). Also, the quantities of butyl acetate required per unit slack wax are 10:1 & 8:1 to obtain paraffin wax with penetration value of 13 by percolation and fractional crystallization techniques respectively (compare PM9 in Table 8 with M6 in Table 6). It is interest to note that fractional crystallization technique is more suitable for deoiling the heavy slack wax by butyl acetate solvent than the percolation technique (Tables 10 and 11 respectively). Whereas by increasing the quantity of the solvent in fractional crystallization technique, the heavy slack wax (wax and entrained oil within and oil outside the wax crystals) is totally dissolved in the solvent by heating till the mixture becomes homogenous. Then the wax is recrystallized by gradual cooling to the desired fractionating temperature (20 C), while in percolation technique the solvent dissolves only the oil outside the wax crystals at the desired percolating temperature
Table 6 Effect of dilution solvent ratio on the physical characteristics, type and molecular type composition of isolated waxes by one stage fractional crystallization of middle slack wax using butyl acetate solvent at fractionating temperature of 20 C and S/F for washing of 2:1 Characteristics Middle Waxes isolated at Slack different Wax dilution solvent to feed ratios (S/F) by using Butyl acetate 2:1 (M4) Congealing point, C Kinematic viscosity at 98.9 C, mm2 s 1 Refractive index at 98.9 C Mean molecular weight Oil content, wt.% Needle penetration at 25 C Color (ASTM-D 1500) Refractive index by TAPPI-ASTM equation Ultraviolet absorbance at 290 nm Molecular type composition Total saturates, wt.% n-paraffins content, wt.% Iso- and cyclo-paraffins content, wt.% Iso- and cyclo-paraffins/ n-paraffins ratio Total aromatics, wt.% Mono-aromatics, wt.% Degree of branching (% CH3 content) Type of wax 59 4.30 1.4270 446 6.23 40 1.5 64 4.19 1.4224 451 1.07 18 1.0 1.4280 4:1 (M5) 65.5 4.22 1.4236 461 0.65 16 0.5 1.4285 6:1 (M6) 67.5 4.38 1.4242 469 0.03 13 0.0 1.4292 0.312

latter case as they have higher refractive indices and viscosities than the other constituents of the wax. Data of molecular type composition confirm the above findings as the iso- and cyclo-paraffins contents of the waxes separated from the three slack waxes are decreased by increasing the dilution or percolation solvent ratios (Tables 1, 4 and 510) and the decrease is more pronounced by using butyl acetate solvent than ethyl acetate solvent (Compare Tables 5 and 6 or 7 and 8). Meanwhile there is a valuable decrease in the mono-aromatic constituents accompanied with the absence of di-aromatic ones for the waxes separated from the heavy slack wax (Tables 9 and 10). Moreover, the degree of branching decreases with increasing dilution or percolation solvent ratios, is mainly due to the decrease of iso-paraffins content for the waxes separated from the three slack waxes (Tables 1, 4 and 510) beside the decrease of aromatics content which is mainly mono-aromatic constituents attached with long side chain for the waxes separated from the middle and heavy slack waxes (Tables 5, 7, 9 and 10). Comparing the effect of increasing the quantity of solvent used in fractional crystallization technique; solvent feed ratios of dilution and washing; with those in solvent percolation technique, it can be noticed that, the two techniques behave the same trend upon increasing the solvent feed ratio as the iso-

96.97 62.89 34.08 0.54 3.03 3.03 10.78

100 79.23 20.77 0.26

100 82.32 17.68 0.21

100 84.10 15.90 0.19

0.00 0.00 0.00 0.00 0.00 0.00 8.70 8.65 7.40 Macro-crystalline

M.T. Zaky et al. / Fuel Processing Technology 88 (2007) 913920 Table 7 Effect of percolation solvent ratio on the physical characteristics, type and molecular type composition of isolated waxes by solvent percolation of middle slack wax using ethyl acetate solvent at percolating temperature of 20 C Characteristics Middle Waxes isolated at different percolation slack solvent to feed ratios (S/F) by using wax Ethyl acetate 6:1 8:1 10:1 12:1 4:1 (PM1) (PM2) (PM3) (PM4) (PM5) Congealing point, C Kinematic viscosity at 98.9 C, mm2 s 1 Refractive index at 98.9 C Mean molecular weight Oil content, wt.% Needle penetration at 25 C Color (ASTM-D 1500) Refractive index by TAPPI-ASTM equation Ultraviolet absorbance at 290 nm Molecular type composition Total saturates, wt.% n-paraffins content, wt.% Iso- and cyclo-paraffins content, wt.% Iso- and cyclo-paraffins / nparaffins ratio Total aromatics, wt.% Mono-aromatics, wt.% Degree of branching (% CH3 content) Type of wax 59 4.3 62 4.11 62.5 4.16 63.5 4.19 64 4.24 64.5 4.26

917

1.4270 1.4224 1.4229 1.4236 1.4239 1.4241 446 6.23 40 1.5 450 1.39 22 455 1.12 19 461 0.68 16 465 0.05 15 465 0.04 15

1.0 1.0 0.5 0.0 0.0 1.4273 1.4275 1.4278 1.4280 1.4282 0.351 0.231 0.220

macro-crystalline waxes; as they characterized by refractive indices lower than those obtained by the equation and by viscosities at 98.9 C lower than 7.4 mm2 s 1; except the waxes (PH1 and PH2) isolated from heavy slack wax by using butyl acetate at percolation solvent ratios of 6:1 and 8:1 by weight (Table 11) lie in the category of semi-microcrystalline waxes as they characterized by refractive indices higher than those obtained by the equation and by viscosities at 98.9 C lower than 10 mm2 s 1. According to petroleum wax specifications, all the tested macro-crystalline waxes lie also in the category of macrocrystalline waxes, except the needle penetration for the separated waxes L1 in Table 1, PL1-PL3 in Table 3, PL6 in Table 4, M1 in Table 5 and H1 in Table 9 are higher than the macro-crystalline wax group limit (22). Different grades of paraffin waxes can be produced from the three slack waxes by using fractional crystallization and solvent percolation techniques at ambient temperature of 20 C and at various solvent to feed ratios. Eleven of fully refined food grade paraffin waxes were separated from the light slack wax as they are white in color

96.67 62.89 34.08 0.54 3.03 3.03 10.78

99.26 74.45 24.81 0.33 0.74 0.74 9.86

100 76.28 23.72 0.31 0.00 0.00 8.80

Table 8 Effect of percolation solvent ratio on the physical characteristics, type and molecular type composition of isolated waxes by solvent percolation of middle slack wax using butyl acetate solvent at percolating temperature of 20 C Characteristics Middle Waxes isolated at different percolation slack solvent to feed ratios (S/F) by using wax Butyl acetate 4:1 6:1 8:1 10:1 12:1 (PM6) (PM7) (PM8) (PM9) (PM10) Congealing point, C Kinematic viscosity at 98.9 C, mm2 s 1 Refractive index at 98.9 C Mean molecular weight Oil content, wt.% Needle penetration at 25 C Color (ASTM-D 1500) Refractive index by TAPPI-ASTM equation Ultraviolet absorbance at 290 nm Molecular type composition Total saturates, wt.% n-paraffins content, wt.% Iso- and cyclo-paraffins content, wt.% Iso- and cyclo-paraffins/ n-paraffins ratio Total aromatics, wt.% Mono-aromatics, wt.% Degree of branching (% CH3 content) Type of wax 59 4.3 64 4.20 64.5 4.22 65 4.24 66 4.30 66 4.30

Macro-crystalline

(20 C) but it can't penetrate them to dissolve the entrained oil. Oil content data confirm the previous findings. Comparing H6 in Table 10 with PH3 in Table 11, it was found that both paraffin waxes are obtained with the same quantity of butyl acetate per unit slack wax (10:1) by fractional crystallization and percolation techniques having oil contents of 0.05 & 2.5 wt.% respectively. Generally, paraffin waxes with different specifications can be produced from different slack waxes by fractional crystallization or percolation technique using ethyl or butyl acetate solvent at different solvent feed ratios and at ambient temperature of 20 C. Thus, paraffin waxes of the same needle penetration of 22, 19 and 15 and having different mean molecular weights and congealing points can be obtained. Compare H2 in Table 9 with both L4 in Table 2 and PL7 in Table 4, compare L2 in Table 1 with both M2 in Table 5 and PM6 in Table 8 and compare also PL10 in Table 4 with PM8 in Table 8 respectively. 3.2. Isolated wax type Examining the isolated wax type in Tables 111 on the basis of TAPPI-ASTM equation, it can be noticed that all the studied waxes isolated from the three slack waxes lie in the category of

1.4270 1.4234 1.4238 1.4244 1.4255 1.4255 446 6.23 40 1.5 459 1.10 19 461 0.85 17 463 0.60 15 469 0.05 13 469 0.02 13

1.0 1.0 0.5 0.0 0.0 1.4280 1.4282 1.4284 1.4287 1.4287

0.364

0.210 0.210

96.97 62.89 34.08 0.54 3.03 3.03 10.78

100 76.52 23.48 0.31 0.00 0.00 9.25

100 83.26 16.74 0.20 0.00 0.00 8.22

Macro-crystalline

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M.T. Zaky et al. / Fuel Processing Technology 88 (2007) 913920 Table 10 Effect of dilution solvent ratio on the physical characteristics, type and molecular type composition of isolated waxes by one stage fractional crystallization of heavy slack wax using butyl acetate solvent at fractionating temperature of 20 C and S/F for washing of 2:1 Characteristics Heavy slack wax Waxes isolated at different dilution solvent to feed ratios (S/F) by using Butyl acetate 8:1 (H3) 69 5.38 1.4274 536 1.69 21 1.0 1.4297 Congealing point, C Kinematic viscosity at 98.9 C, mm2 s 1 Refractive index at 98.9 C Mean molecular weight Oil content, wt.% Needle penetration at 25 C Color (ASTM-D 1500) Refractive index by TAPPI-ASTM equation Ultraviolet absorbance at 290 nm Molecular type composition Total saturates, wt.% n-paraffins content, wt.% Iso- and cyclo-paraffins content, wt.% Iso- and cyclo-paraffins/n-paraffins ratio Total aromatics, wt.% Mono-aromatics, wt.% Di-aromatics, wt.% Degree of branching (% CH3 content) Type of wax 62.5 6.00 1.4402 477 23.05 59 3.0 4:1 (H4) 69.5 5.30 1.4279 533 2.04 15 1.0 1.4299 6:1 (H5) 70.5 5.27 1.4260 535 0.15 12 1.0 1.4303 0.468 8:1 (H6) 71.5 5.20 1.4221 540 0.05 11 0.5 1.4306 0.283

Table 9 Effect of dilution solvent ratio on the physical characteristics, type and molecular type composition of isolated waxes by one stage fractional crystallization of heavy slack wax using ethyl acetate solvent at fractionating temperature of 20 C and S/F for washing of 2:1 Characteristics Heavy slack wax Waxes isolated at different dilution solvent to feed ratios (S/F) by using Ethyl acetate 4:1 (H1) Congealing point, C Kinematic viscosity at 98.9 C, mm2 s 1 Refractive index at 98.9 C Mean molecular weight Oil content, wt.% Needle penetration at 25 C Color (ASTM-D 1500) Refractive index by TAPPI-ASTM equation Ultraviolet absorbance at 290 nm Molecular type composition Total saturates, wt.% n-paraffins content, wt.% Iso- and cyclo-paraffins content, wt.% Iso- and cyclo-paraffins/n-paraffins ratio Total aromatics, wt.% Mono-aromatics, wt.% Di-aromatics, wt.% Degree of branching (% CH3 content) Type of wax 62.5 6.00 1.4402 477 23.05 59 3.0 67 5.50 1.4287 524 6.03 24 2.0 1.4290 6:1 (H2) 68 5.44 1.4282 529 2.22 22 1.5 1.4294

86.18 36.62 49.56 1.35 13.82 11.52 2.30 16.64

96.09 97.98 59.20 62.46 36.89 35.52 0.62 0.57 3.91 2.02 3.91 2.02 0.00 0.00 10.06 8.70 Macro-crystalline

86.18 36.62 49.56 1.35 13.82 11.52 2.30 16.64

97.14 98.84 72.19 74.60 24.95 24.24 0.35 0.32 2.86 1.16 2.86 1.16 0.00 0.00 9.47 8.09 Macro-crystalline

[7], their oil contents less than 0.5 wt.% and their ultraviolet absorbance at 290 nm less than 0.12 [2]. They are as follows: Five paraffin waxes (L2L6) were produced by fractional crystallization technique at ethyl acetate dilution solvent ratios of 6:1 & 8:1 for L2 & L3 respectively (Table 1) and at butyl acetate dilution solvent ratios of 2:1, 4:1 & 6:1 for L4, L5 & L6 respectively (Table 2). Six paraffin waxes (PL4, PL5 & PL7PL10) were produced by solvent percolation technique at ethyl acetate percolation solvent ratios of 12:1 & 14:1 for PL4 & PL5 respectively (Table 3) and at butyl acetate percolation solvent ratios of 6:1 to 12:1 for PL7 to PL10 respectively (Table 4). Six of fully refined grade and nine of semi-refined grade paraffin waxes were isolated from the middle slack wax. They are as follows: Six paraffin waxes (M3, M6, PM4, PM5, PM9 & PM10) are classified as fully refined grade paraffin waxes as their oil contents are less than 0.5 wt.%. M3 & M6 were produced by fractional crystallization technique using ethyl and butyl acetate solvents respectively at dilution solvent ratio of 6:1 (Tables 5 and 6). Meanwhile PM4PM5 & PM9PM10 were obtained by solvent percolation technique using ethyl and butyl acetate solvents respectively at percolation solvent feed ratios of 10:1 & 12:1 (Tables 7 and 8). Nine paraffin waxes (M2, M4, M5, PM1PM3 & PM6PM8) are classified as semi-refined grade paraffin waxes as their

oil contents are higher than 0.5 and less than 1.5 wt.% [1]. M2, M4 & M5 were obtained by fractional crystallization technique at ethyl acetate dilution solvent ratio of 4:1 for M2 (Table 5) and at butyl acetate dilution solvent ratios of 2:1 &
Table 11 Effect of percolation solvent ratio on the physical characteristics and type of isolated waxes by solvent percolation of heavy slack wax using butyl acetate solvent at percolating temperature of 20 C Characteristics Heavy slack wax Waxes isolated at different percolation solvent to feed ratios (S/F) Butyl acetate 6:1 (PH1) Congealing point, C Kinematic viscosity at 98.9 C, mm2 s 1 Refractive index at 98.9 C Mean molecular weight Oil content, wt.% Needle penetration at 25 C Color (ASTM-D 1500) Refractive index by TAPPI-ASTM equation Type of wax 62.5 6.00 1.4402 477 23.05 59 3.0 66.5 5.80 1.4329 514 7.02 32 2.5 1.4289 8:1 (PH2) 67.5 5.60 1.4306 520 5.32 30 2.0 1.4292 10:1 (PH3) 68.5 5.48 1.4289 529 2.5 22 1.0 1.4296 12:1 (PH4) 68.5 5.48 1.4289 529 2.49 22 1.0 1.4296

Semimicrocrystalline

Macrocrystalline

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Fig. 1. Effect of solvent feed ratio on the yield of waxes isolated from light (A), middle (B) and heavy (C) slack waxes. FC: Fractional crystallization technique, P : Percolation technique, EA: Ethyl acetate solvent, BA: Butyl acetate solvent.

4:1 for M4 & M5 respectively (Table 6). Meanwhile PM1 PM3 & PM6PM8 were separated by solvent percolation technique using ethyl acetate solvent for PM1PM3 (Table 7) and butyl acetate solvent for PM6 PM8 (Table 8) at percolation solvent feed ratios of 4:1 to 8:1 for both solvents. Two of fully refined grade and five scale grade paraffin waxes were isolated from the heavy slack wax. They are as follows: - Two paraffin waxes (H5 & H6) are classified as fully refined grade paraffin waxes (ceresins) as their oil contents are 0.15 & 0.05 wt.% and having congealing points of 70.5 & 71.5 C

respectively [10]. They were separated by fractional crystallization technique with butyl acetate solvent at dilution solvent feed ratios of 6:1 & 8:1 respectively (Table 10). - Five paraffin waxes (H2H4, PH3 & PH4) are classified as scale grade paraffin waxes as their oil contents are more than 1.5 and less than 3 wt.%. H2H4 were obtained by fractional crystallization technique at ethyl acetate dilution solvent ratios of 6:1 & 8:1 for H2 & H3 respectively (Table 9) and at butyl acetate dilution solvent ratio of 4:1 for H4 (Table 10). Meanwhile PH3 & PH4; with nearly the same physical

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characteristics; were separated by solvent percolation technique with butyl acetate solvent at percolation solvent feed ratios of 10:1 & 12:1 respectively (Table 11). 4. Conclusions The study shows that fractional crystallization and solvent percolation techniques using ethyl acetate and butyl acetate solvents could be employed for separation of paraffin waxes from light and middle slack waxes. While, solvent percolation technology is preferable due to it eliminates the need of crystallization and filtration steps and saving of time required in solvent fractional crystallization. Also, it was found that fractional crystallization technique is more suitable for deoiling the heavy slack wax by butyl acetate solvent than the percolation technique as by increasing the quantity of the solvent, the solvent dissolves the entrained oil within and oil outside the wax crystals during the re-crystallization step while in percolation technique, the solvent dissolves only the oil outside the wax crystals. References
[1] F. Richter, in: G. Alan (Ed.), Modern Petroleum Technology, vol. 2, Lucas, John Wiley and sons Ltd., on behalf of The Institute of Petroleum, New York, 2000. [2] A. Sequeria Jr., Lubricant Base Oil and Wax Processing, Marcel Dekker, Inc., New York, 1994.

[3] N.H. Mohamed, M.T. Zaky, A.S. Farag, A.F.M. Fahmy, Separation of Paraffin Wax Using Solvent Fractionation. Accepted at 17/3/2006 to be published in Pet. Sci. and Technol. [4] K.M. Agrawal, Y. Kumar, Deoiling of Hard Microcrystalline Wax by Solvent Percolation Technique, Res. Ind. 39 (1994) 209210. [5] Annual Book of ASTM-Standards (American Society for Testing and Materials), Petroleum Products, Lubrications, 1999. West Conshohocken, Sect. 5. [6] S.W. Ferris, Petroleum Waxes, Characterization, Performance and Additives, Technical Association of the Pulp and Paper Industry, Special Technical Association Publication, New York, STAP No. 2, 1963, pp. 119. [7] R.I. Gottshall, C.F. McCue, Petroleum waxes including petrolatums, in: J.P. Allinson (Ed.), Criteria for Quality of Petroleum Products, Applied Science Publishers Ltd., on behalf of The Institute of Petroleum, London, 1973, pp. 209225. [8] L.R. Snyder, in: E. Heftmann (Ed.), Chromatography, Van Nostrand Reinhold Company, New York, 1975. [9] K.M. Agrawal, G.C. Joshi, Microcrystalline Waxes. 1. Investigation on the Structure of Waxes by Proton Nuclear Magnetic Resonance Spectroscopy, J. Chem. Tech. Biotechnol., vol. 31, 1981, pp. 693696. [10] L.P. Kazakova, Investigation and application of solid hydrocarbons from petroleum, Chem. Technol. Fuels Oils 16 (1980) 470476.