Appl. Chem. Eng., Vol. 22, No. 6, December 2011, 664-671

664

- ,

*,

() , *

(2011 8 22 , 2011 9 26 , 2011 11 7 )

-

Structures and Properties of Semi-blown Petroleum Asphalt

Kyung Eui Min and Han Mo Jeong*,

R&D Institute, Korea Petroleum Industrial Co. Ltd., Ulsan 680-090, Korea

*Department of Chemistry, University of Ulsan, Ulsan, 680-749, Korea

(Received August 22, 2011; Revised September 26, 2011; Accepted November 7, 2011)

- ,

, , .

,

. 1H-NMR, ,

. , .

The vacuum residue of petroleum refinery, i.e. asphalt, was modified through a non-catalytic air blowing process to prepare

the semi-blown asphalt. Changes in composition, chemical structure, and physical properties of asphalt were examined. The

result from the thin layer chromatography showed that the asphaltene content in asphalt was increased by the air blowing

on account of the aromatization of aliphatic hydrocarbon and condensation. These changes in molecular structure were also

confirmed by 1H-NMR, differential scanning calorimetry, and thermogravimetry. Because of the molecular structure changes,

the penetration of asphalt was decreased and the softening point and the flash point of asphalt were increased.

Keywords: semi-blown asphalt, air blowing process, asphaltene, molecular structure, thermal properties, physical properties

1. 1)

(asphalt) (bitumen)

,

[1,2].

.

, S, N, O

heterocyclic ,

(Fe, Mg, Ni, Ca ) , porphyrine ,

[2,3].

, .

Saturates-Aromatics-Resines-Asphaltenes analysis (SARA )

n- (maltene)

(asphaltene, As) . ,

n- (saturates, Sa),

(aromatics, Ar),

(e-mail: hmjeong@mail.ulsan.ac.kr)

(alkylated and cycloalkylated aromatic rings)

(resin, Re) .

620

Figure 1

[4].

, Figure 2

,

.

,

[5].

-

(oxidation-polycondensation), (modification),

(vulcanization)

. -

(air blowing) (Figure 3)

, (dehydrogenation or aromatization)

, , , , ,

. , ,

(catalytic air blowing process) -

(full-blown asphalt) ,

665- ,

Appl. Chem. Eng., Vol. 22, No. 6, 2011

Figure 1. Chemical structure of asphaltene.

Figure 2. Sol-gel structure model of asphalt.

Table 1. Physical Properties of Asphalts

Sample Blowing time (min) Penetration (deci-mm)Softening point

Flash point ()Temperature () Increase (/h)

AP-0 0 - - - 250

AP-9 90 265 35 23.3 264

AP-14 140 142 40 17.1 -

AP-18 180 89 44 14.6 265

AP-21 210 69 47 13.4 -

AP-24 240 53 50 12.5 278

Figure 3. Air blowing pilot plant.

- (semi-blown as-

phalt) . - -

. , - -

,

, -

.

, ,

. , -

[6-11], - ,

.

, .

2.

2.1. -

(root) (

(), S50), ( : 15 L, : 0.68 m,

: 2.2 m, inlet nozzle : 5 mm),

25% (Knock-out

vessel, : 2 L, : 0.33 m, : 0.6 m)

- (Figure 3) . SK

(vacuum residue, 70 Saybolt Furol : 100 sec)

80% 12 kg , 220 ,

0.1 kgf/cm2 1.74 m

3/min,

145 L/minkg

. Table 1

. , AP-14 140 min -

.

666

, 22 6 , 2011

(a)

(b)

Figure 4. TLC chromatograms of asphalts : (a) AP-0 and (b) AP-24.

Figure 5. Compositions of asphalts from SARA analysis.

Figure 6. Chemical constituents transitions during air blowing process.

2.2. (Thin layer chromatography, TLC)

TLC , (FID) Iatron Labo-

ratories Inc.() IatroscanTM

MK-6/6S SARA

. , 1 g dichloromethane 100 mL

24 h , ( )

1 h , 1

n- 30 min , 2 20 min ,

/ ( : 95/5) 5 min

3 (triple repeated elution developing)

, FID

.

2.3.

Bruker Avance

III 300 (NMR) . ,

0.005 g C6D6 (shift factor; 1H(7.15)) CS2 10 mL

24 h 5 mm

25 . 1H-NMR (

1H)

300 MHz .

(differential scanning calorimetry, DSC) Netzsch Gera-

tebau GmbH DSC 204 F1 Phoenix (20

mL/min) -100 , 10 /min

200 (Tg) (Tm)

.

(thermogravimetry, TGA) Netzsch Geratebau GmbH

TG 209 F1 Iris , 10.00 mg 30

10 /min 800 .

(Softening point, SP) ASTM D 36 Walter Herzog

GmbH HBR-754 ,

(Penetration, PN) ASTM D 5 Precision 73515

.

(Flash point) ASTM D 92 Instrumentation Scientific

Laboratory (Cleaveland Open Cup,

COC) SC-355 .

3.

3.1.

(Figure 3) TLC

SARA Figure 4 ,

Figure 5 .

(saturates, Sa)

, (aromatics, Ar)

, (resin, Re)

, (asphaltene, As)

. Sa

Sa 220

. , Sa Ar

. Figure 6

, Sa

Ar , Re As

667- ,

Appl. Chem. Eng., Vol. 22, No. 6, 2011

Table 2. Structural Properties of Asphalts

Sample Colloid instability index (Ic) N Hsat/Har

AP-0 0.48 24.9 522

AP-9 0.36 19.0 -

AP-14 0.27 18.2 -

AP-18 0.34 17.8 303

AP-21 0.38 17.7 -

AP-24 0.39 17.2 149

(a) (b) (c)

Figure 7. 1H-NMR spectra of asphalts : (a) AP-0, (b) AP-9, and (c) AP-24.

. Sa

, Ar Re , As

.

Sa As

[8-11], -

. Boduszynski[8]

Sa , Quddus

[9] -

(FeCl3, 0.3 wt%) , 0.002 mL/minkg, ,

240 15 h -

- ,

Sa , (naphthene aromatics, nap-Ar),

(polar-Ar), As ,

, Sa polar-Ar

, Sa, nap-Ar, polar-Ar

As .

, [As+Sa]/[Re+Ar]

(colloidal instability index, Ic) Gaestel [12]

, Ic Table 2 ,

,

.

,

.

,

AP-24 1.8 wt%

, , H2S, CO2, H2O

.

3.2.

1H-NMR Figure 7 ,

(Har) 7.2 ppm ,

(Ho) 5.5 ppm ,

(Hsat) 03 ppm

[13,14]. Hsat ,

- (H) 23 ppm, -

(H) 12 ppm,

- ,

(H) 01 ppm

[16]. 03 ppm

H , -

, N (

). Table 2 ,

N , aromaticity . 23 ppm

N, O, S heteroatom

, heteroatom

6% [9]. heteroatom

H2O, SO2 ,

.

N H .

Figure 7(a) Har 6.87.5 ppm

7.16 ppm ,

, C6D6

. Har Hsat

(Hsat/Har) 1H-NMR

, CS2 1H-NMR

Hsat/Har Table 2 . Table 2

,

. Figure 1

sp2

Har .

668

, 22 6 , 2011

(a)

(b)

Figure 8. DSC thermograms of asphalts : (a) AP-9 and (b) AP-24.

Table 3. Thermal Properties of Asphalts

AsphaltTg Tm

Tg () Cp (J/gK) Tm () Hm (J/g)

AP-9 -1.3 0.388 40.1, 60.0, and 75.3 1.469

AP-14 3.8 0.269 40.3, 62.6, and 75.9 1.685

AP-18 7.4 0.247 42.5, 65.3, and 76.1 1.897

AP-21 8.7 0.229 42.5, 64.8, and 76.7 2.143

AP-24 10.3 0.193 42.5 and 74.3 2.359

1H-NMR , Hsat Har

, Table 2 Hsat/Har

[15]. Hsat/Har

.

3.3.

AP-9 DSC thermogram Figure 8(a) , -1.3

(Tg) ,

,

[17,18]. Figure 8(b)

AP-24 DSC thermogram

.

Table 3 ,

Tg , Tg (Cp)

.

,

. Masson

Tg Sa -88-60 , Ar -34-15 , Re

1020 , As 4060 ,

AP-9 Strategic Highway

Research Program (SHRP) Performance Grading (PG )

(Materials Reference Library (MRL) ; AAN)

Tg -19 [19]. , Adedeji

AP-21 PG ( MRL ; AAE-1)

Tg -2.9 [20], Memon AP-18 PG

(SHRP PG-(58-10)) Tg -9.2 [21]

.

PG Tg .

(Tm) (Hm)

.

(

)

,

,

.

TGA Figure 9 ,

. 200

(highly volatile

matter, HV) , 250500

(medium volatile

matter, MV) , -

, 550650

(combustible materials, CM)

. (residuals,

RD) (ash) . HV

200 Sa Ar , MV Ar

Re , CM

Re As . Table 4

HV MV , CM

RD .

, .

Freeman-Carroll[22] (1)

.

(1)

w t , Wr , Ea

(J/mol), T (K), R (8.314 J/mol

669- ,

Appl. Chem. Eng., Vol. 22, No. 6, 2011

Table 4. The Results by TGA

SampleComposition (wt%)

Highly volatile matters Medium volatile matters Combustible materials Residuals

AP-0 30.9 67.6 1.4 0.1

AP-9 13.3 79.8 3.8 3.1

AP-14 2.1 81.9 8.9 7.1

AP-18 2.0 68.3 22.4 7.3

AP-21 0.6 67.2 23.0 9.2

AP-24 0.0 60.8 24.1 15.1

(a)

(b)

Figure 9. TGA thermograms of asphalts : (a) AP-9 and (b) AP-24.

Figure 10. Freeman-Carroll plots of TGA data : () AP-14, ()

AP-18, () AP-21, and () AP-24.

K), n .