Characteristics of the Hydrocracked Products and Asphaltene with Con-

version in a Vacuum Residue Hydrocracking with MoS2 Dispersed Cata-

lyst
Kang Seok Go1,2, Suk Hyun Im3,4, Nam Sun Nho2,3, Yong Ku Kim2,3, Kwang Ho Kim2,3, Woo Hyun Kim2,3 and Sung Woo Jeong2, (1)Korea Institute of Energy Research, Deajeon,
Korea, The Republic of, (2)Korea Research Institute of Chemical Technology, Daejeon, Korea, The Republic of, (3)Korea Institute of Energy Research, Daejeon, Korea, The
Republic of, (4)University of Science and Technology, Daejeon, Korea, The Republic of

Back-
ground During reaction of cracking
Sludge
Asphaltene
(sediment, coke)

*process-heating Homepage *Janus Energy Resources Homepage

*Hypothetical condensed asphal-

*Petroleum Energy Center, Ad-
Slurry phase hydrocracking Problem tene molecular structure ( Asok
Kumar Tharanivasan, Ph.D., The-
vanced Catalysts Research Labora-
tory(Hiroiku Kawai et al. 1998)
sis, U.Calgary, 2012)

*Capable of handling heavy oil *Heavy oil contains a lot of asphaltenes Objective
*Higher conversion than others process *Asphaltenes cause formation of sedi- *Find the characteristics of the hydrocracked prod-
*Dispersion catalyst shows high catalytic ments and coke at a higher conversion ucts with different catalyst concentration and con-
activity and good performance. *Sediments or coke deposit on the cata- version
lyst surface cause fouling in the *Study on the characteristics of asphaltene during
Experimental & Con- process phase separation
cept
Feed property Batch reactor Hydrocracked product Extraction procedure

𝐻2
Feed VR
API Gravity 5.84
Gas
Micro Carbon Residue Content,
wt%
20.5 Vacuum Slurry phase hydrocracking Asp
SG at 15.5℃ 1.0303 residue
Sat. 4.3 +
Aro. 56.4
Dispersion Change of reaction condition Liquid Extract
Resin 19.4
Asphal. 19.8 catalyst asphaltene
Sulfur, wt.% 6.7 Find the characteristics of the hydroc- sediments
Nickel, wt.ppm 40 racked products and asphaltene
Vanadium, wt.ppm 126 Coke

Reaction condition Analysis of product Analysis of asphaltene

*Temperature: 385~440℃ *Simdis: ASTM7500 *NMR: 500MHz H-NMR(BRUKER)
*Reaction time: 4h *XRF(OXFORD) *M.W.: Gel Permeation Chromatography(WATERS)
*Catalyst concentration: 100~10000ppm *Gas Chromatography(agilent) *E.A.: C, H, N, S-Organic Elemental Analyzer(Thermo Scientific FLASH EA-2000)/
*Initial pressure: 80bar at 80 ℃ O- Elemental Analyzer (Thermo Finnigan FLASH EA-1112)

Re-
sult Trend in the characteristics of the asphaltene according to variation of convers
Characteristics of the hydrocracked products 0.95 1 1200.6

0.95
0.9
1000.6
100.0 100.0 0.60
0.9
RG (the ratio of i-C4H10 yield to n-C4H10 yield)

0.85
0.55
800.6
Aromaticity index of Asp.

0.85
Resid conversion (524'C+, wt.%)

80.0 0.50 0.8

M.W (g/mol)
H/C ratio

80.0 0.8 600.6

0.45
0.75
HDS(wt.%)

0.75
60.0 0.40 400.6
0.7
0.7
0.35
60.0
200.6
0.65
0.30 0.65
40.0

0.25 0.6 0.6 0.6

20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0

40.0 Resid 전환율 (524'C+, wt.%) Resid 전환율 (524'C+, wt.%) Resid 전환율 (524'C+, wt.%)
20.0 0.20
380 390 400 410 420 430 440 450 20.0 40.0 60.0 80.0 100.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0

Temp. ('C) Resid conversion(524'C+, wt.%) Resid conversion(524'C+, wt.%)

*Symbol
Relation between temperature and conversion Effect of catalyst concentration Effect of catalyst concentration
with different catalyst concentration on the HDS according to variation
of conversion
on the RG value according to
variation of conversion
Differences on asphaltene in liquid and in sediments with different temperature
*Slurry-phase hydrocracking of heavy oil and
model reactant: effect of dispersed Mo catalyst-
Hui Du et al
100.0 100.0 Ca/Ct(fa), Aromaticity Index CP/CA(x), Condensation Index of Aromatic RA,U, No. Aromatic Rings per Unit
10.0
Sheet
0.84 0.48 17.00
90.0
Asphaltene removal ratio in the liquid(wt%)

8.0 0.82 0.46 15.00

90.0 80.0

0.80 0.44 13.00

70.0
Liquid yield (wt.%)

Coke yield (wt.%)

6.0

80.0 60.0 0.78 0.42 11.00

4.0
50.0 9.00
0.76 0.40

70.0 40.0
0.74 0.38 7.00
2.0

30.0
5.00
0.72 0.36 100ppm 500ppm 500ppm 1000ppm
100ppm 500ppm 500ppm 1000ppm 100ppm 500ppm 500ppm 1000ppm
60.0 20.0 at 410℃ at at at
0.0 at at at at at at at at
20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 410℃ 425℃ 425℃
410℃ 410℃ 425℃ 425℃ 410℃ 410℃ 425℃ 425℃
Resid conversion(524'C+, wt.%) Resid conversion(524'C+, wt.%) Resid conversion (524'C+, wt.%) Asp. In Liquid Asp. In Sediments.
Asp. In Liquid Asp. In Sediments.
Asp. In Liquid Asp. In Sediments.

Relation between conversion and As-

phaltene removal ratio with different
*Symbol catalyst concentration
Avg. M.W, g/mol, H/C atomic ratio
700.00 0.82

0.80
650.00

Conclusion
0.78
600.00
0.76

550.00
0.74

500.00 0.72

• The conversion increased with increasing reaction temperature. The desulfurization rate in- 450.00
0.70

0.68

creased with conversion and catalyst concentration, and i-C4 gas production increased with in-
400.00
0.66

350.00
0.64

creasing catalyst concentration. 300.00

100ppm
at
500ppm
at
500ppm
at
1000ppm
at
0.62
100ppm
at
500ppm
at
500ppm
at
1000ppm
at
410℃ 410℃ 425℃ 425℃ 410℃ 410℃ 425℃ 425℃

• The change of liquid and coke yields was dramatic at about conversion 80%, Also, the asphal- Asp. In Liquid Asp. In Sediments. Asp. In Liquid Asp. In Sediments.

Asphaltene in liquid Asphaltene in sedi-

tene removal ratio in the liquid was greatly increased. -> precipitated asphaltene ments

• The change of asphaltene characteristics according to the conversion was found, and the dif- • RA,U/Aromaticity/Molecular weight increase
• H/C ratio, condensation index decrease
ference of asphaltenes in liquid and in sediments was found to be similar at high temperature • At lower temperature, the differences is greater