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PDVSA
I - OBJECTIVE .............................................................................................................................. 1 II - PROCESS ................................................................................................................................. 1 III - EFFECTS OF DEASPHALTING ON THE PHYSICO-CHEMICAL CHARACTERISTICS OF THE DEASPHALTED OIL ................................................................................................... 1 IV - PROCESS FLOW...................................................................................................................... 5 V - PROPANE DEASPHALTING UNIT - SINGLE EFFECT EVAPORATION................................. 7
1 2 3 Deasphalting circuit ...................................................................................................................... 7 Solvent recovery from the asphaltic phase ..................................................................................8 Solvent recovery from the oil phase .............................................................................................8
17/01/2005
I-
OBJECTIVE
The process is used for manufacturing bright stock for lube oil refining, for preparing lube hydrocracker feed, fuels hydrocracker feed and catalytic cracker feed. The process produces also asphalt which may be used as a blending component of bitumen, as a fuel oil blending component, as a feedstock to a heavy oil conversion unit such as a coker or a gasification by partial oxidation. The process may be used to upgrade heavy crude oil.
II -
PROCESS
The vacuum residue has the form of a colloidal solution composed of a continuous oily medium containing micellae or aggregates of juxtaposed heavy molecules called asphaltenes. They contain carbon and hydrogen and many hetero-atoms such as sulfur, nitrogen and metals. The addition of light liquid paraffins to this solution greatly modifies the characteristics of the oily medium, causing precipitation of the asphaltenes and sometimes even of the resins. The deasphalting uses light paraffins as an antisolvent for asphaltenes. It is a liquid-liquid separation operation that extracts the last of the easily convertible hydrocarbons from the vacuum residue. Solvents employed are light paraffins: propane, butane and pentane. The lower molecular weight hydrocarbons have the lower solvent power and will precipitate more asphalt. The yield in deasphalted oil increases with the molecular weight of the solvent, but its quality decreases. Although the process is primarily used to remove asphatic materials from the feedstock, it also removes other undesirable materials such as sulfur, nitrogen, aromatics and metals. The wax content of the deasphalted oil increases. Propane is more suited for the manufacture of lube feedstocks because greater quantities of the asphaltenes and resins must be removed to produce a quality base oil as compared to preparation of cracking feedstocks. Butanes and pentanes are generally used to prepare FCC and hydrocracker feedstocks because they provide a higher yield of deasphalted oil, and precipitate less of the asphalt than does propane. The use of heavy solvent results in rock asphalt being produced.
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WAXES
RESINS
Normal paraffins
LUBOIL BASES
Highly branched-chain naphthenes and prarffins C12 C C12 C10 iC15 C C5 CH V C iC5 C10 iC15 C10 C10 C iC10 C10 C C5 C C N H C C S C CH3 iC10 Highly branched-chain aromatics CH3 C
n = 50 to 100
C C12 iC10
CH3
(CH CH2)n
CH3
D PPC 1003 A
CH3
CH
(CH2)n
CH3
CH3
ASPHALTENES
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ASPHALTENES*
WAXES
SOLVENTS FEED Yields Specific gravity Viscosity at 100 Conradson carbon Asphaltenes (insoluble C7 ) Nickel Vanadium Sulphur Nitrogen cSt % wt % wt ppm ppm % wt % wt % weight 100 1.003 345 16.4 4.2 19 61 4.05 0.29
C3 RAFFINATE 45.15 0.939 35 1.65 < 0.05 1 1.4 2.55 0.12 ASPHALTENIC COMPOUNDS
C4 RAFFINATE 70.10 0.959 63 5.3 < 0.05 2 2.6 3.3 0.19 ASPHALTENIC COMPOUNDS 1.102 0 110 5.8
C5 RAFFINATE 85.50 0.974 105 7.9 < 0.05 7 15.5 3.65 0.22 ASPHALTENIC COMPOUNDS 1.140 0 155 6.4
1.063 11 59 5.3
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The temperature and dosage are the process conditions which are varied with feedstock quality and deasphalted oil quality requirements.
- decreases: viscosity index At constant solvent to feed ratio, increasing temperature: - decreases: DAO yield DAO SG DAO viscosity DAO carbon Conradson DAO metals, sulfur and nitrogen
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IV - PROCESS FLOW
Feed and light paraffinic solvent are mixed then charged to an extractor. The extractor is a vertical tower containing baffles or a rotating disc contactor RDC. The feed enters at the middle of the extractor and the solvent near the bottom. The solvent riche phase (extract) consisting of deasphalted oil and solvent leaves the top of the treating tower. The solvent lean phase (raffinate) consisting of asphalt and solvent leaves from the bottom of the treating power. Different types of solvent recovery are used: - conventional: single or multiple effect evaporation - supercritical: ROSE TM (Residuum Oil Supercritical Extraction) process licensed by Kellogg Brown & Root, Inc. DEMEX UOP A description of a deasphalting unit with single effect evaporation is given in paragraph V and with supercritical solvent recovery in paragraph VIII.
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D PCD 076 B
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55 to 70C
40 to 50C
ASPHALT
V-
PROPANE DEASPHALTING UNIT - SINGLE EFFECT EVAPORATION 1DEASPHALTING CIRCUIT (see figure on page 9)
The feed arrives from the refinery storage tanks at the pump intake at a temperature of 120C. The pump then discharges it through a flow controller into a shell and tubes cooler in which the temperature is lowered to 71C, then through the shell of a second air cooler in which the temperature is further lowered to 53C. Between the outlet of the first cooler and the inlet of the second one it is possible to inject liquid propane at 50C into the product to adjust its viscosity before it enters the second cooler. The product then enters the extraction column at a temperature of 53C at one of the two inlets. The lower inlet is located about halfway up the column, and the upper one about two thirds of the way up. The asphaltenic content of the raw material generally governs the inlet used. If the asphaltenic content is high and requires a longer contact time, the upper inlet is used. On the contrary, if asphaltenic compounds are entrained in the column overhead then the lower inlet should be used. On entering the column the feed is dispersed by the distribution rack to ensure an even distribution throughout the column which is equipped with trays that promote good countercurrent contact between the oil and the ascending propane. The oil containing the asphaltenic compounds, resins and other undesirable substances flows down the column and contacts the ascending liquid propane which enters the bottom of the column below the lowest plate. When the cold propane encounters the oil circulating in the column, more and more of the undesirable components are dissolved in the ascending current of propane. It is only in the lower part of the column that the asphaltenic compounds contained in the oil are not dissolved in the propane. The asphaltenic compounds continue to descend to the bottom of the column where they are drawn off, via a flow controller and a level controller, and sent to solvent recovery and separation of the asphaltic phase. The propane solution continues towards the top of the column where it is reheated by the steam circulating in a system of four coils installed inside the column. Since the propane solution is reheated, the relatively insoluble products are removed from the solution. These products form a secondary phase containing the resins which have properties intermediate between those of the asphaltenic compounds and those of the oil. The resins flow downwards and encounter the ascending current of propane containing the dissolved oil. The resins are gradually dissolved in the propane solution. This repeated action of dissolving and precipitating generates the reflux in this part of the column. At the point where the feed enters the column the resins which have not already been dissolved are entrained by the descending current of asphaltenic compounds and are gradually washed as the asphaltic phase descends to the bottom of the column. The asphalt-free oil continues to the top of the column where it is drawn off via a pressure controller and sent to solvent recovery and separation of the oil phase. The previously mentioned steam coils are designed to maintain a temperature gradient between the feed inlet and the top of the column.
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2-
3-
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24
24
D PCD 1181 A
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0.07 20 C3 1.2 Flow rate (t/h) Water 15 DEASPHALTED OIL STRIPPER 150 200 108 MP Steam To B.D 18 30 % 0.6 16 DEASPHALTED OIL 16 CONDENSOR 0.02 Temperature (C)
65
30
Deasphalted oil + C3
Steam
EXTRACTION COLUMN
53
0.8 0.07 19 50 PROPANE ACCUMULATOR 19 260 120 MP Steam EVAPORATOR 250 0.4 Fluxing gas oil 11 COMPRESSOR ASPHALT STRIPPER
45
40
120
Feed
45
10
1-
2-
EXTRACTION TEMPERATURE
Propane behaviour above 40C is the opposite of that of usual solvents such as furfurol, NMP, etc. which have a capacity to dissolve oils that increases with the operating temperature. Above 40C the capacity of propane to dissolve oils decreases as the temperature rises. This is because as propane nears its critical temperature of 97C it gradually regains its gas properties. Its surface tension and its solvent capacity decrease. It can thus be seen that as the temperature rises the proportion of asphalt at the bottom of the column increases whereas that of deasphalted oil decreases. The asphalt is softer and softer since it is increasingly diluted by the oil fractions that are insoluble in the propane at the operating temperature. These results are shown on the graphs. It can be seen that the percentage of deasphalted oil obtained is proportionately smaller when the temperature of the mixture is higher, and that the ring and ball softening point of the precipitated asphalt is proportionately lower when the temperature is higher. Consequently, to obtain the highest possible yield of deasphalted oil a large proportion of propane has to be used in relation to the raw material and the operating temperature should be moderate.
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11
70
60
52 C
50
40
Deasphalted oil, weight %
65 C
30
80 C
20
10
10
12
14
16
18
20
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D ANA 013 C
12
82
52 C
77
71
65 C
65
60
80 C
55
49
D ANA 1000 A
43
10
12
14
16 Propane Residue
18
20
ratio
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13
The table below gives the main characteristics of the vacuum residue of a Near East crude oil and of the two products resulting from the propane deasphalting operation.
RESIDUE % of feed Density at 15C Flash point Engler viscosity at 100C Viscosity index after dewaxing at -12C Freezing point Total sulphur content Penetration at 25C R & B softening point 5 250 to 300 37 100 1020 290 155
5.78 14 61
3-
Top of column
Column bottom
WAXES
LUBOIL BASES
RESINS
T = To
ASPHALTENES
T < To T > To
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D PCD 1182 A
14
TRAYS
T = 65
Case 2
Case 1
50
60
Asphalt settling
Steam
Resin recycle and washing 45
Predilution
Settling
Temperature (C)
Vacuum residue
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15
DAO STRIPPER
PITCH
DAO
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D PCD 1183 A
16
Taking into example the Arab Light DAO characteristics given in page 4: - a VGO-C3 DAO blend can be processed on a conventional FCC - a VGO-C4 DAO blend can be processed on a FCC able to handle heavy feed - a VGO-C5 DAO cannot be processed on a conventional FCC an is at the upper limit of a FCC with cat cooler However, the compliance with an overall gasoline limit of 50 ppm (or less) will require to reduce the sulfur level of FCC gasoline. The FCC-feed pretreating is a possible route to lower gasoline sulfur with the advantages of increasing the FCC gasoline yields (hydrogenation of aromatics to paraffins) and reducing the sulfur content of the LCO.
HDT VGO
ATM. RESID
VACUUM DISTILLATION
C5 C4 C3
FCC
Naphtha Diesel
D PCD 1184 A
FCC feed preheating It is also possible, as described in the chapter on hydrocracking technologies to achieve some conversion in the FCC pretreater (MHDC) to produce a good quality Diesel.
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