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WO2017112611A2 - Procédé de séparation d'un mélange - Google Patents

Procédé de séparation d'un mélange Download PDF

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Publication number
WO2017112611A2
WO2017112611A2 PCT/US2016/067646 US2016067646W WO2017112611A2 WO 2017112611 A2 WO2017112611 A2 WO 2017112611A2 US 2016067646 W US2016067646 W US 2016067646W WO 2017112611 A2 WO2017112611 A2 WO 2017112611A2
Authority
WO
WIPO (PCT)
Prior art keywords
mixture
centrifuging
time period
mixing
surfactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2016/067646
Other languages
English (en)
Other versions
WO2017112611A3 (fr
Inventor
Nirmal Tatavalli-Mittadar
Michael Joseph Doll
Paul Lee TORTORICI
Denise Dudley CANSLER
Lori Ann Crom
Heejae HUH
Carmen Geraldine REZNIK
Thomas Carl Semple
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Shell USA Inc
Original Assignee
Shell Internationale Research Maatschappij BV
Shell Oil Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV, Shell Oil Co filed Critical Shell Internationale Research Maatschappij BV
Publication of WO2017112611A2 publication Critical patent/WO2017112611A2/fr
Publication of WO2017112611A3 publication Critical patent/WO2017112611A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/10—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for with the aid of centrifugal force
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0217—Separation of non-miscible liquids by centrifugal force
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water

Definitions

  • This invention relates to a method of separating a mixture comprising an aqueous component, a hydrocarbon component and a surfactant component using one or more centrifuging steps.
  • Phase behavior testing of chemical enhanced oil recovery mixtures involves determining the measurement of the number of phases at equilibrium, the equilibrated phase volumes, their appearance, mixing and wetting properties and physical properties such as interfacial tension and viscosity.
  • components are mixed in a tube. The tube is placed in a vertical position and the equilibrated phases are allowed to separate at a designated temperature.
  • the invention provides a method of separating a mixture comprising an aqueous component, a hydrocarbon component and a surfactant component comprising the step of centrifuging the mixture for a first time period to separate the mixture.
  • the invention also provides a method of performing a salt scan of a surfactant/oil mixture comprising: a) preparing a number of sample mixtures by mixing a hydrocarbon, a surfactant and a number of brines having different salinity and salt components; b) centrifuging each of the samples for a time period to separate the mixture into its respective phases; and c) determining the optimal salinity of the surfactant in the hydrocarbon by observing the phase separation of the mixture.
  • the invention provides an improved method to conduct phase behavior testing of mixtures useful in chemical enhanced oil recovery (cEOR).
  • Phase behavior testing can take weeks or even months to get results as the mixture is allowed to equilibrate until it separates into its respective phases.
  • the phase behavior test can be seen as a series of steps, including phase contacting and equilibration; and separation of the equilibrated phases. It is believed that the separation of the equilibrated phases takes the longest amount of time.
  • the time required for the phase separation step is reduced by use of a centrifuge, but the other steps of phase contact and new phase formation are not conducted in the centrifuge.
  • the phase contact step can be carried out by mixing or by adjusting the temperature of the mixture.
  • phase behavior tests can be reduced from weeks or months to hours or days.
  • use of this method allows smaller sample sizes and less expensive testing equipment to be used.
  • phase behavior tests can be used to conduct quality control on surfactants by measuring their performance and to screen new surfactants or screen existing surfactants for use in new hydrocarbon formations.
  • the mixture of components for the phase behavior test is prepared by mixing an aqueous component, a hydrocarbon component and a surfactant component.
  • other components may be added or may be present in one of the other components, including pH modifiers, pH buffers, cosurfactants, cosolvents, components used in surfactant synthesis, polymers, and viscosity modifiers.
  • the aqueous component may contain salt and/or other components.
  • the aqueous component is preferably brine.
  • the brine is preferably similar to brine found in that formation.
  • the hydrocarbon component may be any hydrocarbon.
  • the hydrocarbon component is preferably liquid under the testing conditions.
  • the hydrocarbon component may be a mixture of different hydrocarbons.
  • the hydrocarbons may be substituted with other compounds, including sulfur, nitrogen and oxygen.
  • octane is the preferred hydrocarbon component.
  • crude oil may be used as the
  • Crude oil contains a number of different hydrocarbons as well as other non-hydrocarbon components.
  • the hydrocarbon component is preferably an organic phase with a density that is less than the density of water.
  • the surfactant component may comprise any surface-active component that is useful in enhanced oil recovery.
  • the surfactant component may comprise internal olefin sulfonates, alcohol alkoxy carboxylates, alcohol alkoxy sulfates, alcohol alkoxy glycerol sulfonates, secondary alcohol alkoxy derivatives, aryl alkyl sulfonates, alkyl aryl sulfonates or mixtures thereof.
  • the mixture may comprise one or more optional components.
  • optional components include pH modifiers, for example, inorganic acids, organic acids, inorganic bases, organic bases, and salts of acids or bases; pH buffers, for example, inorganic and organic components; cosurfactants, for example, alcohol alkoxylates; cosolvents, for example, alcohols; components used in surfactant synthesis, for example, organic acids or alcohol alkoxylates; polymers, for example, HP AM, PEG, PPG, APG; and viscosity modifiers, for example, diols, ethers, alcohols and alcohol alkoxylates.
  • pH modifiers for example, inorganic acids, organic acids, inorganic bases, organic bases, and salts of acids or bases
  • pH buffers for example, inorganic and organic components
  • cosurfactants for example, alcohol alkoxylates
  • cosolvents for example, alcohols
  • components used in surfactant synthesis for example, organic acids or alcohol alkoxylates
  • polymers for example, HP AM, PEG, PPG, A
  • the mixture In the initial preparation of the mixture, it is important to ensure that there is sufficient contact between the three or more components. Any mixing step that imparts sufficient agitation to the mixture is suitable.
  • the mixture can be mixed by hand, using a vortex generator, vortexer, or using another mechanical device that mixes the components of the mixture.
  • the mixture can be prepared by adding the components to a container
  • the surfactant component is mixed with the aqueous component before the hydrocarbon component is added to the mixture.
  • the centrifuging step of this method can be carried out in any centrifuging device that can safely handle the mixture described above.
  • the centrifuge is an apparatus that rotates an object, in this case, a container with the mixture, around a fixed axis. This rotation applies a strong force perpendicular to the axis of spin.
  • the centrifuge causes denser substances to move outward in the radial direction and less dense substances to move towards the center.
  • the centrifuging step provides an increased driving force to separate the phases of different densities.
  • the centrifuging step may be carried out for a time period of from about 3 seconds to about 20 hours.
  • the time period for the centrifuging step is preferably of from about 5 minutes to about 4 hours, more preferably of from about 5 minutes to about 60 minutes.
  • the amount of time required for this step will depend largely on the sample size used. For example, if a capillary tube was used with a small sample size, the time period could be on the order of microseconds.
  • the centrifuging step is normally carried out under ambient pressure as the mixture is prepared and placed in a container that is then sealed. The pressure can however be increased and the mixture injected into the container at a higher than ambient pressure.
  • the temperature of the mixture may be from 0 °C to 120 °C.
  • the temperature of the mixture is preferably in the range of from 20 °C to 100 °C.
  • the mixture may be at one temperature before the centrifuging step and the temperature may be increased or decreased during the centrifuging step.
  • the mixture may be at ambient temperature at the beginning of the centrifuging step, and the temperature may be increased during the centrifuging step.
  • the temperature, after it has been increased, may also be decreased during the centrifuging step. Cycling the temperature can be used to remove kinetic barriers to equilibrium.
  • the temperature is increased to match the temperature observed in a hydrocarbon formation. If the pressure in the container is higher than ambient pressure then the suitable temperature ranges would also increase, but this is known to one of skill in the art. Further, it may not be practical to pressurize the centrifuge container.
  • the mixture may be mixed to increase the phase contacting.
  • This mixing step may be carried out in a similar manner to the original mixing used to form the mixture or using a different method.
  • the mixing step may be done by hand or using a mechanical mixing apparatus.
  • the mixing step can be carried out by or enhanced by adjusting the temperature of the mixture.
  • the mixing may be carried out for a time period of from 3 seconds to about 20 hours.
  • the mixing time period is preferably in a range of from about 5 minutes to about 4 hours and more preferably in a range of from 5 minutes to about 60 minutes.
  • the mixing may be carried out at the same temperature as the centrifuging step or the temperature may be increased or decreased before mixing.
  • the mixture may be centrifuged again in a second centrifuging step that is carried out in a similar manner to the first centrifuging step.
  • the second centrifuging step may be carried out under different conditions and/or for a different time period than the first centrifuging step.
  • the revolutions per minute of the centrifuge may be changed for different centrifuge steps.
  • the mixture may be centrifuged, mixed, centrifuged, mixed and centrifuged to obtain the desired separation.
  • the final step is preferably a centrifuging step.
  • the number of steps of centrifuging and mixing, and the time periods for each to arrive at an optimal separation may differ for mixtures containing different components, i.e., different crude oils, aqueous brines or different surfactants.
  • the centrifuging steps are all carried out for the same amount of time.
  • all but the final centrifuging step are carried out for the same amount of time.
  • the final centrifuging step may be carried out for a longer or shorter period of time.
  • the mixture may be separated using the following steps:
  • One potential use of this method is to perform a salinity scan of a specific surfactant and hydrocarbon mixture.
  • the centrifuging steps and mixing steps can be carried out according to any of the embodiments described above.
  • a skilled person can determine the optimal salinity of the surfactant in the tested brine- hydrocarbon mixtures. As the separated mixtures are observed, those with low salinities will have a micro-emulsion in the aqueous phase and these are referred to as under optimal, Winsor Type I or II(-). Those with optimal salinities will have three phases and these are referred to as Winsor Type III. As the salinity increases further, the micro-emulsion is in the oleic phase, and this is referred to as an over optimal or Winsor Type II or II(+) system. Examples
  • Example 2 the separation of the same mixtures as used in Example 1 was carried out without using a centrifuging step.
  • the surfactant was mixed with NaCl brines in tubes such that each tube contained a surfactant-brine mixture of a different brine concentration.
  • Octane was added to the mixtures of surfactant and brine in each tube.
  • the final NaCl brine concentration which was the same as that used in Example 1 is shown in Table 2.
  • the sample tubes with surfactant, brine, and octane were shaken and placed into an oven at 90 °C. After 1 week, the sample tubes were removed from the oven, observed visually, shaken, and placed back in the oven at 90 °C.
  • centrifuging step can provide similar results to those seen when using the typical test where the phases are allowed to separate with gravity.
  • the centrifuging step can be carried out at different temperatures, for different time periods and at different revolutions per minute to optimally separate the mixture.
  • sample tubes were centrifuged for a first time period, shaken, centrifuged for a second time period, shaken, centrifuged for a third time period, shaken and then centrifuged for a final time period.
  • the shaking steps were carried out by vigorous hand shaking. After the final centrifugation step, the samples were evaluated visually to determine the phase separation.
  • Sample tubes with salinities of about 9.5-11.5 wt% NaCl were under optimal as shown by a light yellow to yellow hazy aqueous phase, indicating the presence of the surfactant microemulsion in the aqueous brine phase.
  • Sample tubes with salinities of 12-13 wt% NaCl had 3 phases.
  • the optimal salinity was determined to be 12 wt%.
  • the solubilization of oil and water phases at the optimal salinity also referred to as the solubilization parameter, was determined to be ⁇ 7 mL/mL.
  • Example 2 the separation of the same mixture as used in Example 2 was carried out without using a centrifuging step.
  • the surfactant was mixed with NaCl brines in tubes such that each tube contained a surfactant-brine mixture of a different brine concentration.
  • Octane was added to the mixtures of surfactant and brine in each tube.
  • the final NaCl concentration in the tubes ranged from 9.5-13 wt%, with each tube having 0.5 wt% more NaCl than the previous tube.
  • sample tubes with surfactant, brine, and octane were shaken and placed into an oven at 90 °C. Each week for a total of 3 weeks, the sample tubes were removed from the oven, observed visually, shaken, and placed back in the oven at 90 °C.
  • Sample tubes with salinities of about 9.5-11.5 wt% were under optimal with a light yellow to yellow hazy aqueous phase, indicating the presence of the surfactant microemulsion in the aqueous brine phase.
  • Sample tubes with salinities of 12-13 wt% NaCl had 3 phases.
  • the optimal salinity was determined to be 12 wt%.
  • the solubilization of oil and water phases at the optimal salinity also referred to as the solubilization parameter, was determined to be ⁇ 7 mL/mL.
  • mixtures were separated using centrifugation.
  • An alcohol alkoxy sulfate surfactant (Ci 2 -Ci 3 branched alcohol with 13 propoxylate groups) was mixed with brine from formation A and alcohol co-solvent in 3 tubes such that each tube contained a surfactant-co-solvent-brine mixture of unique co-solvent concentration.
  • Crude oil from formation A was added to the mixtures of surfactant, co-solvent, and brine in each tube.
  • the final co-solvent concentration in the tubes ranged from 0.5% to 2.0 wt%, with each tube having 0.5 wt% co-solvent more than the previous tube.
  • the sample tubes with surfactant, co-solvent, brine, and crude oil were mixed using a vortexer.
  • the temperature used for centrifugation was about 20-25 °C.
  • the sample tubes were centrifuged for a first time period, shaken, centrifuged for a second time period, shaken, centrifuged for a third time period, shaken and then centrifuged for a final time period.
  • the shaking steps were carried out by vigorous hand shaking.
  • Sample tubes with co-solvent concentrations of 0.5-2.0 wt% had 3 phases, indicating desired surfactant solubilization of crude and brine phases.
  • Example 3 the separation of the same mixture as used in Example 3 was carried out without using a centrifuging step.
  • the phase behavior of the same Ci 2 -Ci 3 alcohol alkoxy sulfate surfactant and alcohol co-solvent with crude and brine from the same hydrocarbon formation A was analyzed using the conventional method of phase behavior testing.
  • the surfactant was mixed with formation brine and alcohol co-solvent in 3 tubes such that each tube contained a surfactant-co-solvent-brine mixture of unique co- solvent concentration. Crude oil was added to the mixtures of surfactant, co-solvent, and brine in each tube.
  • the final co-solvent concentration in the tubes ranged from 0% to 1.5 wt%, with each tube having an additional 0.25-0.5wt% co-solvent than the previous tube.
  • the sample tubes with surfactant, co-solvent, brine, and crude were shaken and allowed to equilibrate at room temperature of about 20-25 °C. Each week for about 3 weeks, the sample tubes were observed visually, shaken, and allowed to equilibrate again at room temperature.
  • Sample tubes with co-solvent concentrations of 0.5%- 1.5 wt% had 3 phases, indicating desired surfactant solubilization of crude and brine phases.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

L'invention concerne un procédé de séparation d'un mélange comprenant un composant aqueux, un composant hydrocarboné et un composant tensioactif comprenant l'étape de centrifugation du mélange pendant une première durée pour séparer le mélange. Un procédé de mise en œuvre d'un balayage du sel dans un mélange tensioactif/huile est en outre décrit, ledit procédé comprenant : a) la préparation d'un certain nombre de mélanges d'essai par mélange d'un hydrocarbure, d'un tensioactif et d'un certain nombre de saumures ayant une salinité et des composants de sels différents; b) la centrifugation de chacun des échantillons pendant une durée apte à séparer le mélange en ses phases respectives; et c) la détermination de la salinité optimale du tensioactif dans l'hydrocarbure par observation du mélange qui se sépare en trois phases.
PCT/US2016/067646 2015-12-22 2016-12-20 Procédé de séparation d'un mélange Ceased WO2017112611A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562270607P 2015-12-22 2015-12-22
US62/270,607 2015-12-22

Publications (2)

Publication Number Publication Date
WO2017112611A2 true WO2017112611A2 (fr) 2017-06-29
WO2017112611A3 WO2017112611A3 (fr) 2017-09-08

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Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2249741B (en) * 1990-10-06 1994-06-29 Univ Bradford Separation of the components of liquid dispersions
GB9905668D0 (en) * 1999-03-12 1999-05-05 Univ Napier Method
US8518243B2 (en) * 2004-10-01 2013-08-27 Saudi Arabian Oil Company Method for utilizing hydrocarbon waste materials as fuel and feedstock
US7612117B2 (en) * 2005-11-17 2009-11-03 General Electric Company Emulsion breaking process
IT1396957B1 (it) * 2009-12-18 2012-12-20 Eni Spa Procedimento per il trattamento di residui oleosi provenienti dall'industria petrolifera

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