Refining-Petrochemicals-Chemicals-Engineering

PDVSA

Process Engineering Applied To Petroleum Refining Module 8: REFINING PROCESSES (2)

VACUUM RESIDUE DEASPHALTING

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

VI - IMPROVEMENTS TO THE PROCESS..................................................................................... 8 VII - INFLUENCE OF THE OPERATING CONDITIONS ................................................................ 10

1 2 3 Proportion of propane versus vacuum residue (dilution) ............................................................ 10 Extraction temperature ...............................................................................................................10 Influence of the temperature gradient ........................................................................................ 13

VIII - SUPERCRITICAL SOLVENT RECOVERY ............................................................................. 15

RA DAS - 00029_A_A - Rev. 0

17/01/2005

2005 ENSPM Formation Industrie - IFP Training

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.

III - EFFECTS OF DEASPHALTING ON THE PHYSICO-CHEMICAL CHARACTERISTICS OF THE DEASPHALTED OIL

The purpose of deasphalting is to remove the heaviest and most aromatic molecules. Consequently, the effects on the deasphalted oil in relation to the vacuum residue are as follows: density decreases viscosity decreases significantly viscosity index tends to increase carbon residue decreases the color is improved sulfur content decreases metal content decreases

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2005 ENSPM Formation Industrie - IFP Training

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

Aromatics and heterocyclic compound

Condensed polyaromatics Metal compounds Ni 2

n = 50 to 100

C C12 iC10

CH3

(CH CH2)n

CH3

* in colloidal state ** in solution

D PPC 1003 A

2005 ENSPM Formation Industrie - IFP Training

C

CH3

CH

(CH2)n

CH3

CH3

ASPHALTENES

00029_A_A

LUBOIL BASES RESINS**

ASPHALTENES*

WAXES

DEASPHALTING OF ARABIAN LIGHT VACUUM RESIDUE Influence of the solvent

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

Specific gravity Penetration at 25C Softening points C Sulphur %

1.063 11 59 5.3

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2005 ENSPM Formation Industrie - IFP Training

DEASPHALTING PROCESS VARIABLES: influence of the solvent

Deasphalting conditions Solvent dosage Temperature Pressure vol. % C bars

C3 500-1000 45-90 30-45 40

C4 400-700 80-130 30-40 70

C5 300-500 140-210 20-40 85

Yields (% wt) Examples

The temperature and dosage are the process conditions which are varied with feedstock quality and deasphalted oil quality requirements.

DEASPHALTING PROCESS VARIABLES: effect of solvent to feed ratio and temperature

At content temperature, increasing solvent to feed ratio: - increases: DAO yield DAO SG DAO viscosity DAO carbon residue DAO metals, sulfur and nitrogen

- 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

- increases: viscosity index

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2005 ENSPM Formation Industrie - IFP Training

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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2005 ENSPM Formation Industrie - IFP Training

Asphalt 70% Propane 30%

D PCD 076 B

00029_A_A

Deasphalted oil + propane

30 bar

55 to 70C

Deasphalted oil / Propane separation

DEASPHALTED OIL D.A.O.

Steam Heating area by steam coils Propane

FEEDSTOCK VACUUM RESIDUE

EXTRACTION COLUMN Dilution rate 5 to 12/1 Propane Propane

2005 ENSPM Formation Industrie - IFP Training

40 to 50C

Asphalt / Propane separation

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-

SOLVENT RECOVERY FROM THE ASPHALTIC PHASE

The bottom product from the extraction column is composed of approximately 70% asphaltenic compounds and 30% propane. The product leaves the bottom of the extraction column under level and flow control at a temperature of 45C and enters a furnace which heats the mixture to a temperature of around 260C. The asphalt mixture is then sent to the evaporator, which operates at a pressure of 19 bar gauge. All the propane, except for a very small amount (about 2%), that was previously dissolved in the asphaltic phase, is removed in the form of gas at 260C. It leaves the evaporator via the gas line, through the cooler to return in liquid form to the propane accumulator FA-1. The pressure in the accumulator is 18 bar gauge and the temperature is 50C. The asphaltenic compounds are liquid at 260C and still contain a very small amount of propane. The phase enters the stripper, which operates more or less at atmospheric pressure, at the level of the top tray. The steam and gaseous propane from the stripper are routed to the condenser. Before entering the condenser, the gases are mixed with the steam and propane from the deasphalted oil stripper. The mixture enters the condenser at a temperature of 200C. The steam free gaseous propane leaves the top of the condenser to the compressor inlet. The propane is compressed to the same pressure as that of the accumulator, after which the gas is condensed and cooled from 82C to 50C so that it can return to the accumulator. The propane is ready to enter the extraction column again and the cycle is complete.

3-

SOLVENT RECOVERY FROM THE OIL PHASE

The deasphalted oil and propane solution, commonly known as the deasphalted oil mixture, leaves the top of the column at around 65C and the pressure controller reduces the pressure from 30 to around 20 bar gauge. After this reduction in pressure the deasphalted oil mixture enters the evaporators. The propane gas goes to the propane condenser where it is condensed, and then returns to the accumulator at a temperature of 50C. The deasphalted oil stripper is designed to remove the propane from the oil by steam injection. The propane-free deasphalted oil leaves the bottom of the stripper and is sent to the intermediate product storage tanks. The propane and steam mixture leaves the top of the stripper and is sent to the condenser, as mentioned above. Before entering the condenser it is joined by an identical product from the asphalt stripper.

VI - IMPROVEMENTS TO THE PROCESS

The most significant progress has been made in energy consumption in particular, with marked reductions (about 50% of a single flash vaporization) through propane recovery via flashes at 2 pressure levels. Processes known as supercritical processes exist. They separate liquid propane by settling and require very little heat.

00029_A_A

2005 ENSPM Formation Industrie - IFP Training

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ASPHALT or BITUMEN 160

VACUUM RESIDUE FEED

24

D PCD 1181 A

00029_A_A

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)

PROPANE DEASPHALTING UNIT

Pressure

65

30

Deasphalted oil + C3

Steam

EXTRACTION COLUMN

Steam reheating coils

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

2005 ENSPM Formation Industrie - IFP Training

40

120

Feed

Asphalt + C3 70% 30%

45

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VII - INFLUENCE OF THE OPERATING CONDITIONS

Pressure does not affect product quality provided that it is high enough to maintain the propane in liquid state.

1-

PROPORTION OF PROPANE VERSUS VACUUM RESIDUE (dilution)

Increasing the proportion of propane in relation to the residue increases the yield of deasphalted oil. Parallel to this increase in the proportion of propane, and consequently in the yield, the molecular weight, the specific gravity, the viscosity and the Conradson carbon content of the oil also increase. At the same time the softening point of the precipitated asphalt increases with the proportion of propane to residue. The following graphs show the propane-residue ratio on the abscissa and the oil yield and the precipitated asphalt melting point on the ordinate. It can be seen that at a given operating temperature the oil yield effectively increases with dilution, as does the asphalt softening point.

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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2005 ENSPM Formation Industrie - IFP Training

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OIL YIELD AS A FUNCTION OF THE PROPANE/RESIDUE RATIO

70

60
52 C

50

40
Deasphalted oil, weight %

65 C

30

80 C

20

10

10

12

14

16

18

20

Propane ratio Residue

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2005 ENSPM Formation Industrie - IFP Training

D ANA 013 C

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ASPHALT MELTING POINT AS A FUNCTION OF THE PROPANE/RESIDUE RATIO

82

52 C
77

71

65 C

R and B softening point of asphalt

65

60

80 C
55

49
D ANA 1000 A

43

10

12

14

16 Propane Residue

18

20

ratio

00029_A_A

2005 ENSPM Formation Industrie - IFP Training

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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

DEASPHALTED OIL 29.80 930 279 4.75 78 + 51 2.90

ASPHALTENIC COMPOUNDS 70.20

5.78 14 61

3-

INFLUENCE OF THE TEMPERATURE GRADIENT

Establishing a temperature gradient in the column creates a reflux of the heavy fractions of the deasphalted oil and improves separation as shown in the diagram below.

Top of column

Column bottom

WAXES

LUBOIL BASES

RESINS

T = To

ASPHALTENES

T < To T > To

Operation without temperature gradiant

With temperature gradiant The temperature at the bottom of the column is low in order to ensure good solvent capacity for paraffinic components, and the temperature at the top is higher to improve selectivity for separating the aromatic components. The temperature gradient may be modulated, as illustrated by the two cases shown in the following figure in which the results are slightly different. Case 1 will have a slightly lower yield and a darker colour than case 2 .

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2005 ENSPM Formation Industrie - IFP Training

D PCD 1182 A

14

PROPANE DEASPHALTING COLUMN

TRAYS

T = 65

Deasphalted oil + majority of propane (light phase)

Resin removal Steam reheating coils

Case 2

Case 1

50

60
Asphalt settling

Steam
Resin recycle and washing 45

Predilution

Settling

Propane (light phase) Feed Feed flow rate

D PCD 080 A

Temperature (C)

Vacuum residue

Asphalt and propane (heavy phase)

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2005 ENSPM Formation Industrie - IFP Training

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VIII - SUPERCRITICAL SOLVENT RECOVERY

The process flow of the supercritical solvent recovery processes ROSETM and DEMEX are very similar. The DAO and solvent are separated under supercritical conditions. As the temperature increases above the critical point, the density of the solvent significantly decreases to values approaching that of dense gases. The oil is virtually insoluble in the solvent as a supercritical fluid and a phase separation occurs. The DA oilsolvent passes into a settler for separation of the DA oil and solvent as separate liquid. The energy requirement is significantly reduced compared to the flash vaporization method. The solvent from the asphalt rich phase is recovered in the usual manner. The supercritical solvent recovery has a greater energy saving as the molecular weight of the solvent increases. This is the reason why propane deasphalting generally uses the conventional flash vaporization with double or triple effect evaporation.

Supercritical DAO flow diagram - UOP DEMEX

DAO SEPARATOR EXTRACTOR VACUUM RESIDUE CHARGE PITCH STRIPPER

DAO STRIPPER

PITCH

DAO

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2005 ENSPM Formation Industrie - IFP Training

D PCD 1183 A

16

IX - DAO AS A FCC FEEDSTOCK COMPONENT

To be a suitable FCC feedstock, the DAO must meet the following specs: nitrogen < 2000 ppm carbon Conradson < 2% for a conventional FCC carbon Conradson < 7% FCC for an heavy feed FCC (with dispersion steam, catalyst cooler) metals < 25 ppm

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

DAO Vacuum residue DAO DAO DEASPHALTING HDT

FCC

C3 Asphalt C4 Asphalt C5 Asphalt

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.
00029_A_A

2005 ENSPM Formation Industrie - IFP Training