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US20060118467A1 - Method of transporting heavy crude oils in dispersion - Google Patents

Method of transporting heavy crude oils in dispersion Download PDF

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Publication number
US20060118467A1
US20060118467A1 US10/522,021 US52202105A US2006118467A1 US 20060118467 A1 US20060118467 A1 US 20060118467A1 US 52202105 A US52202105 A US 52202105A US 2006118467 A1 US2006118467 A1 US 2006118467A1
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United States
Prior art keywords
particles
asphaltenes
suspension
effluent
viscosity
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Abandoned
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US10/522,021
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English (en)
Inventor
Jean-Francois Argillier
Isabelle Henaut
Patrick Gateau
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IFP Energies Nouvelles IFPEN
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Individual
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Assigned to INSTITUT FRANCAIS DU PETROLE reassignment INSTITUT FRANCAIS DU PETROLE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GATEAU, PATRICK, HENAUT, ISABELLE, ARGILLIER, JEAN-FRANCOIS
Publication of US20060118467A1 publication Critical patent/US20060118467A1/en
Abandoned legal-status Critical Current

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
    • F17D1/00—Pipe-line systems
    • F17D1/08—Pipe-line systems for liquids or viscous products
    • F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity

Definitions

  • the present invention relates to the sphere of transportation of viscous effluents, notably crudes referred to as “heavy” crudes, for example because of their asphaltenes content.
  • slurry is a suspension or a dispersion of solid particles in a liquid that can be circulated, notably by pumping.
  • This slurry flow type is already commonly used during estuary or river dredging operations, and in the mining industry. What is most interesting is that it allows to transport a maximum amount of solid spoils with as little pumping energy as possible.
  • Concerning the petroleum industry, slurry transportation is used to enrich fuels with coal particles and thus to increase their calorific value.
  • the solid content can reach 60% by mass while keeping acceptable flow properties.
  • the present invention thus relates to a method of transporting a viscous petroleum effluent in pipes. According to the invention, the following stages are carried out:
  • the separation stage can be carried out by adding an amount of n-alkane such as butane, pentane, heptane.
  • the particles can be removed from the fluidized liquid phase.
  • the colloidal elements acting on the viscosity can be asphaltenes.
  • the particles can be dispersed through mechanical mixing.
  • the temperature of said circulating suspension can be controlled in order to slow down the dissolution of the particles in the effluent.
  • the temperature of the suspension can be kept below 40° C.
  • Said particles can be encapsulated after separation.
  • Said particles can be chemically modified prior to being dispersed in the fluidized effluent.
  • An additive can be added to disperse said particles.
  • a predetermined amount of a diluent for said liquid phase can be added.
  • a badly-solubilizing diluent can be selected for said particles.
  • the precipitated asphaltenes can be added in proportions ranging between 1 and 30% by mass.
  • FIG. 1 compares colloidal and slurry solutions
  • FIGS. 2 and 2 a show the evolution of a slurry as a function of time
  • FIGS. 3 and 4 show the influence of shear on a slurry
  • FIGS. 5 and 5 a show the influence of temperature on a slurry
  • FIGS. 6 a and 6 b show the efficiency of the encapsulation of asphaltenes.
  • the present invention preferably applies to heavy crudes. It thus consists in modifying the structural organization of the heavy crude which behaves like a viscous colloidal suspension, to obtain a suspension of non-colloidal particles of lower viscosity.
  • the particles concerned by this change are, within the context of a preferred embodiment of the present invention, asphaltenes. Asphaltenes are molecules of higher molecular weight contained in some crude oils. They are characterized by their high polarity and by the presence of polycondensed aromatic rings. The overlap of these particles spread out in the crude is greatly responsible for the high viscosity of the heavy crudes. This overlap can be eliminated by keeping the asphaltenes in form of solid particles precipitated in the crude.
  • This configuration change can be obtained by deasphalting the crude, then by dispersing the precipitated asphaltenes in the base liquid, notably under strong mechanical stirring.
  • a non limitative method of operation has been developed and it has been checked that the resulting morphology change of the crude in suspension form actually leads to a viscosity decrease.
  • the protocol of the preferred embodiment first requires deasphalting the crude. Methods already exist to carry out this operation.
  • the asphaltene particles are transported in solid form in the crude base liquid in which these asphaltenes are dispersed so that the liquid obtained is more fluid than the original crude.
  • transportation by pumping through the pipes is facilitated up to the refining plants.
  • the slurry is either fed as it is in these treating plants, or after a stage of separation of the suspended solid particles, the asphaltenes, which can simplify the downstream processes.
  • the asphaltenes are precipitated by means of pentane according to the American standard ASTM 893-69. Once filtered (by means of sintered material of porosity 4) and dried (at 80° C. for 2 hours), the particles are crushed (centrifugal ball crusher Retsch S 1000, 15 minutes at 350 rpm), then screened between 100 and 500 ⁇ m.
  • the asphaltenes are dispersed in the deasphalted crude with a mechanical agitator RW20 IKA, at 1200 rpm for 20 minutes.
  • the stirring paddle is selected for its high shearing power. It is a “bow tie” type serpentine paddle which allows excellent dispersion by means of the turbulence zone existing between its coils.
  • the temperature of the sample is kept at 40° C. In each case described hereafter, 25 g product are prepared.
  • Test 1 Comparison of Two Samples, One in Colloidal Suspension Form and the Other in Slurry Form
  • the other by heating to 80° C. for 1 hour, which leads to a product in colloidal solution form.
  • the viscosity is substantially that of a crude having 10% asphaltenes.
  • a natural asphaltene-containing crude (with 17% by mass of asphaltenes) is compared with a slurry obtained as above, but comprising 17% by mass of asphaltenes.
  • the two samples were heated to 40° C. for 20 minutes.
  • the colloidal crude has a viscosity of 345 Pa ⁇ s, whereas the slurry has a viscosity of 95 Pa ⁇ s.
  • the efficiency of the method is clearly shown since the viscosity decrease is significant. It can be noted that the viscosity of the slurry in this case is relatively high for efficient transportation, a dilution would therefore be necessary.
  • FIG. 2 shows the evolution of the viscosity of slurry 3 as a function of time.
  • the various curves ( 3 to 8 ) show a progressive redissolution of the asphaltenes, which is translated into a viscosity rise up to the viscosity value of colloidal solution 9 .
  • FIG. 4 shows that, under such test conditions, no increase in viscosity V is observed during shearing for about 8 hours.
  • 5 a shows the effect of temperature on a sample after 24 hours. Slurrying the heavy crude can require additional precautions or specific treatments to block or to slow down the dissolution of the asphaltenes in the crude if it has to be transported at a temperature above 40° C.
  • the asphaltenes can be advantageously encapsulated prior to being mixed with the crude.
  • the complex coacervation method was used, described for example by J. Richard and J.-P. Benoît in “Microencapsulation”—Techniques de l'In deciur: Goue des Procédés; J 2 210, 1-20.
  • the experimental protocol used is as follows: two 100-ml solutions, one containing 1% gelatin, the other 1% arabic gum, are prepared in milli-Q water and maintained at 40° C. The pH value of these two solutions is adjusted to 6.5.
  • the asphaltenes are then dispersed in the gelatin solution using a Heidolph agitator for 30 minutes, still at 40° C. A stirring rate of the order of 700 min ⁇ 1 is used. This is followed by a dropwise addition of the arabic gum solution (about 3 ml per minute). Then, the pH value of the mixture is adjusted to 4.5 by means of a 10% acetic acid solution (predetermined volume). In order to allow the coacervate droplets to settle around the oil drops, stirring is maintained constant for one hour. Finally, the temperature of the system is lowered to 8° C. to allow the coacervate to gel.
  • FIG. 6 a shows the structure of the encapsulated asphaltene suspension after 1 day and after 36 days. The results show that encapsulation has been efficient to block dissolution of the asphaltenes, the slurry configuration remaining intact after more than 30 days at a temperature of 40° C. A slight viscosity rise (from 50 Pa ⁇ s to 60 Pa ⁇ s) is observed.
  • FIG. 6 b shows the structure of the non-encapsulated asphaltene suspension at the same times: the structure is no longer of the suspension type, and the viscosity becomes very high again.
  • the precipitated asphaltenes are modified by acrylic acid.
  • the acid adsorbed on the asphaltenes is then polymerized. 4 grams acrylic acid and 4 grams heptane are therefore added to 4 grams asphaltenes obtained by heptane precipitation and dried for two hours under vacuum.
  • the suspension is stirred for two hours at ambient temperature in an inert atmosphere (argon).
  • the excess acrylic acid is eliminated by filtration and the solid fraction is suspended again in 8 grams heptane.
  • 0.04 g azo-bis-isobutyronitrile the suspension is maintained for 4 hours at 60° C. under stirring, still in an inert atmosphere.
  • the modified asphaltenes are dried for 2 hours at 80° C.
  • a slurry (sample No.1) consisting of 2 grams modified asphaltenes and 18 grams deasphalted crude is prepared according the procedure already described above.
  • Another slurry (sample No.2) containing 2 grams non-modified asphaltenes and 18 grams deasphalted crude is prepared in parallel. These two slurry samples are stored at 80° C. and the evolution of their viscosity is monitored in the course of time.
  • Modification of the asphaltenes allows to better control their capacity to be dissolved in the deasphalted crude.
  • a slurry (sample No.3) consisting of 2 grams modified asphaltenes and 18 grams deasphalted crude is prepared according to the procedure already described.
  • a slurry (sample No.4) containing 2 grams non-modified asphaltenes and 18 grams deasphalted crude is prepared in parallel. These two samples are stored at 80° C. and the evolution of their viscosity is monitored in the course of time.
  • sample No.3 remains approximately two times lower than that of sample No.4 after a week's storage at 80° C. Storage time at 80° C. (h) 0 2 5 170 Sample Viscosity at 20° C. (Pa ⁇ s) No. 3 26 75 103 104 No. 4 43 132 194 202
  • the method according to the invention can thus be clearly improved by treating the asphaltenes after their precipitation from the crudes.

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  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Water Supply & Treatment (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Colloid Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Pipeline Systems (AREA)
US10/522,021 2002-07-24 2003-07-08 Method of transporting heavy crude oils in dispersion Abandoned US20060118467A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0209407 2002-07-24
FR0209407A FR2842885B1 (fr) 2002-07-24 2002-07-24 Procede de transport des petroles bruts lourds sous forme de dispersion
PCT/FR2003/002115 WO2004011359A2 (fr) 2002-07-24 2003-07-08 Procede de transport des petroles bruts lourds sous forme de dispersion

Publications (1)

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US20060118467A1 true US20060118467A1 (en) 2006-06-08

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US10/522,021 Abandoned US20060118467A1 (en) 2002-07-24 2003-07-08 Method of transporting heavy crude oils in dispersion

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US (1) US20060118467A1 (fr)
CN (1) CN1742071A (fr)
AU (1) AU2003273425A1 (fr)
BR (1) BRPI0312888A2 (fr)
CA (1) CA2493688C (fr)
FR (1) FR2842885B1 (fr)
MX (1) MXPA05000852A (fr)
WO (1) WO2004011359A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110127196A1 (en) * 2004-12-07 2011-06-02 Institutfrancais Du Petrole Viscous Hydrocarbon Treatment Method by In-situ Asphaltene Inerting
WO2012044046A3 (fr) * 2010-09-29 2012-06-07 Sk Biopharmaceuticals Co., Ltd. Nouveaux dérivés de méthylcyclohexane et leurs utilisations
US9028680B2 (en) 2010-10-14 2015-05-12 Chevron U.S.A. Inc. Method and system for processing viscous liquid crude hydrocarbons

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4572781A (en) * 1984-02-29 1986-02-25 Intevep S.A. Solvent deasphalting in solid phase
US5948242A (en) * 1997-10-15 1999-09-07 Unipure Corporation Process for upgrading heavy crude oil production

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8313712D0 (en) * 1983-05-18 1983-06-22 British Petroleum Co Plc Coal oil fuel
GB8318313D0 (en) * 1983-07-06 1983-08-10 British Petroleum Co Plc Transporting and treating viscous crude oils

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4572781A (en) * 1984-02-29 1986-02-25 Intevep S.A. Solvent deasphalting in solid phase
US5948242A (en) * 1997-10-15 1999-09-07 Unipure Corporation Process for upgrading heavy crude oil production

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110127196A1 (en) * 2004-12-07 2011-06-02 Institutfrancais Du Petrole Viscous Hydrocarbon Treatment Method by In-situ Asphaltene Inerting
WO2012044046A3 (fr) * 2010-09-29 2012-06-07 Sk Biopharmaceuticals Co., Ltd. Nouveaux dérivés de méthylcyclohexane et leurs utilisations
US9028680B2 (en) 2010-10-14 2015-05-12 Chevron U.S.A. Inc. Method and system for processing viscous liquid crude hydrocarbons

Also Published As

Publication number Publication date
CN1742071A (zh) 2006-03-01
FR2842885A1 (fr) 2004-01-30
CA2493688C (fr) 2011-10-25
AU2003273425A8 (en) 2004-02-16
WO2004011359A3 (fr) 2004-05-27
BRPI0312888A2 (pt) 2017-05-02
AU2003273425A1 (en) 2004-02-16
MXPA05000852A (es) 2005-04-19
CA2493688A1 (fr) 2004-02-05
FR2842885B1 (fr) 2004-09-10
WO2004011359A2 (fr) 2004-02-05

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Owner name: INSTITUT FRANCAIS DU PETROLE, FRANCE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ARGILLIER, JEAN-FRANCOIS;HENAUT, ISABELLE;GATEAU, PATRICK;REEL/FRAME:016928/0648;SIGNING DATES FROM 20050101 TO 20050130

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