WO2014008559A1 - Processo para a separação de fases de emulsões do tipo água-em-óleo por aplicação indirecta de ultrassom - Google Patents
Processo para a separação de fases de emulsões do tipo água-em-óleo por aplicação indirecta de ultrassom Download PDFInfo
- Publication number
- WO2014008559A1 WO2014008559A1 PCT/BR2012/000235 BR2012000235W WO2014008559A1 WO 2014008559 A1 WO2014008559 A1 WO 2014008559A1 BR 2012000235 W BR2012000235 W BR 2012000235W WO 2014008559 A1 WO2014008559 A1 WO 2014008559A1
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- Prior art keywords
- emulsion
- separation
- water
- process according
- oil
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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
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/02—Dewatering or demulsification of hydrocarbon oils with electrical or magnetic means
-
- 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
- B01D17/06—Separation of liquids from each other by electricity
Definitions
- the present invention is applicable in the area of petroleum production and refining and relates to a process for the separation of water-in-oil (A / O) emulsion phases by the indirect application of ultrasound (US), often between 10 kHz and 1,000 kHz.
- US ultrasound
- the separation of water and oil in production units is essential for oil to meet the specifications defined by the refineries for water and salt content, so that it can be transported from the production unit to the refining unit.
- the fluids find a space where low speeds and high residence time allow the coalescence and sedimentation of most of the drops, which constitutes a free aqueous phase that is removed from the process. In this step also occurs the separation of gases.
- the oil leaving the gravitational separator can then go to an electrostatic handler, in which an electrode-created electric field promotes shock, coalescence, and removal of even dispersed smaller water droplets.
- Ultrasound (US) studies have demonstrated the potential of an alternative and innovative process for separating emulsified water in petroleum.
- the present invention describes a process for separating the phases of A / O type emulsions by indirectly applying US between 10 kHz and 1,000 kHz.
- the US is applied to an intermediate fluid that transmits the US vibrations to the emulsion to be treated, destabilizing the emulsion and causing the separation of the oily and aqueous phases that make up the emulsion.
- the described process may be employed in batch or continuous systems, pressurized or not, and may or may not be associated with the addition of demulsifying agent and heating.
- the described process can be applied in refineries to promote sludge or slop separation, or in the oil desalting step.
- Chinese document CN 2296230 describes an emulsion breaking device in which US is applied directly.
- the invention consists of a small vessel installed upstream of an electrostatic dehydrator in which US is applied to the emulsion before it is fed to the dehydrator.
- CN 200940134 describes an external ultrasonic injection device for dehydrating crude oil by breaking down emulsions and removing mixed water in petroleum, where the transducer is installed on the sidewall of the vessel and the oil is directly demulsified.
- the emulsion separation device includes a separation tank containing the emulsion and at least one ultrasonic oscillating means disposed on the tank wall.
- US 7,708,895 B2 describes emulsion emulsion demulsification by applying US in a current parallel to the emulsion flow. After demulsification, the emulsion is gravitationally separated into an electric field.
- the present invention relates to a process for separating the phases of water-in-oil emulsions in which ultrasound is indirectly applied to an emulsion at a frequency between 10 kHz and 1,000 kHz by means of a fluid. intermediate leading US.
- Figure 1 is a schematic representation of the flow system employed in the process of separating the phases of water-in-oil emulsions by the indirect application of US of the present invention.
- Figure 2 is a schematic representation of the open batch system employed in the process of separating the phases of water-in-oil emulsions by the indirect application of US of the present invention.
- the present invention is a process for phase separation of water-in-oil emulsions by applying US at a frequency between 10 kHz and 1,000 kHz indirectly.
- the water-in-oil (W / O) emulsion consists of the intimate mixture between an aqueous phase and an oil phase, so that the aqueous phase (dispersed phase) drops are dispersed and stabilized in the oil phase (water phase). by the deposition of surfactants at the droplet interface.
- the oil phase may be a natural or synthetic mineral, vegetable or animal oil.
- the aqueous phase may consist of water or a solution having dissolved salt concentrations in a range ranging from 0 to 280,000 mg / L.
- the present invention preferably applies to emulsions in which the oil phase is a natural mineral oil such as petroleum (crude oil) or distillates and the aqueous phase is a saline solution, more specifically salt water from the reservoir from the oil. which oil is produced.
- the ratio of aqueous phase in the emulsion may range from 0.5 to 85% by volume.
- the droplet size of the aqueous phase is variable, but is between 0.01 ⁇ and 1,000 ⁇ in diameter.
- the emulsion which is contained in a storage tank (1), is displaced and / or pressurized by a pump (2) and flows through a pipe until a vase (3).
- the vessel (3) has two compartments, one of which is a coil (5), which connects to the pipe that carries the emulsion; and the space between the serpentine outer wall and the vessel wall, which is filled with a fluid (4).
- Fluid (4) should be efficient in the transmission of ultrasonic energy, such as water, saline water, organic solvents, oils or petroleum emulsion.
- fluid (4) is water.
- the emulsion flows from the tubing into the coil (5) of the vessel (3) and is surrounded by the fluid (4) without direct contact between the fluid and the emulsion.
- US generating devices (6) are attached to the vessel wall (3) so as to transmit US directly to the fluid and, indirectly, to the coil (5) containing the emulsion.
- US generating devices (6) useful for the present invention are any devices capable of generating US at a frequency of 10 kHz to 1,000 kHz and transmitting it to the fluid, since in the present invention the US is used as the driving force for the process of phase separation of the emulsion, no matter how the US is generated or produced.
- Such devices (6) are generally transducers consisting of piezoelectric or piezoceramic materials and have the property of contracting and expanding according to the applied electric field, generating mechanical vibrations at specific frequencies. Thus, transducers convert electrical energy into mechanical energy.
- the transducers when applied in the present invention, may be welded directly to the outer walls of the vessel (3) or there may be an intermediate piece that conducts or concentrates the ultrasonic energy, promoting its transmission to the vessel walls (3).
- the emulsion leaves the vessel (3) through the tubing and proceeds to a resting tank (8), in which the separation is completed by the gravitational field acting on the coalesced droplets.
- the resting tank (8) the emulsion is allowed to remain for a long enough residence time to allow the settling of the drops and separation of the aqueous phase.
- the emulsion Prior to flowing into the resting tank (8), the emulsion may be subjected to any other process or technology conventionally used in the pre-stage primary oil processing (7) in order to accelerate coalescence and phase separation.
- any other technologies capable of promoting the grouping of coalesced droplets may be associated to the formation of a free and easily separable aqueous phase in the resting tank (8).
- These technologies include centrifugation, gravitational separation, ultrasound, hydrocyclones, electrostatic separation, filtration, membrane separation or any combination of these.
- the vessel (3) has inlet and outlet in order to treat an emulsion that continuously flows through it (flow system).
- the vessel (11) may still be closed to treat A / O emulsion batches (12) while receiving ultrasonic vibrations transmitted by the fluid (10).
- the vessel (3, 11) may be pressurized to an absolute pressure ranging from 0 kPa to 20,000 kPa and heated at a temperature ranging from 10 ° C to 270 ° C.
- Pressurization is particularly important in situations where the emulsion consists of a low density, high volatile petroleum, when more volatile components may vaporize due to natural temperature rise due to US absorption.
- Pressurization is also important to inhibit water evaporation with increasing temperature. Evaporation of water is not desired because, while allowing water to be removed, it eventually concentrates the salts in the remaining liquid. As concomitant removal of water and salts contained in the oil emulsion is desired, the separation promoted by the US must occur by a process of droplet coalescence and sedimentation.
- the separation of coalesced droplets can also be enhanced by coupling a centrifugation process.
- the described process can be further combined with other processes aimed at primary petroleum processing based on electrostatic separation or use of microwave radiation.
- the proposed invention may be applied as an isolated process or may be combined with other existing technologies to increase the phase separation efficiency.
- the invention may be applied on varying scales and thus the US application power, flow rates and time intervals may vary depending on the amount of emulsion to be treated.
- the separation efficiency of the aqueous phase which is achieved by the process of the present invention may be determined by the percentage ratio between the volume of separated aqueous phase and the volume of aqueous phase initially present in the emulsion used as filler.
- the US bath is a commonly used equipment for different purposes and consists of a metal tub, on whose outer faces of the walls the US transducers are welded and into which a fluid is placed.
- the parts or bottles, which are to be apply US, are immersed in the fluid contained in the vat.
- the cup horn system is a system that has some features common to US baths and has as a differential a higher concentration of ultrasonic energy in its main compartment.
- the US is generated by a transducer located at the base of the equipment and is transmitted through the metal part of the device (probe or probe) to the conical part that forms the bottom of the fluid compartment.
- the emulsion to be treated was subjected to US application in conical bottom graduated flasks to allow easy measurement of water which is separated during and after treatment.
- the tests were performed with a water-in-oil (W / O) type synthetic emulsion generated from a 17 ° API petroleum and containing 50% v / v aqueous phase.
- the aqueous phase used was a saline solution with a concentration of 100 g / l NaCl, since the forming water that normally constitutes natural petroleum emulsions has dissolved salts, often in high concentrations.
- the emulsion preparation procedure consisted of incorporating 532 g of saline into 473 g of petroleum (17 ° API) using a pendular stirring oven (heating at 80 ° C and 100 bpm). After stirring in the oven, the mixture was sheared with a high power mechanical stirrer for 3 minutes at 7700 rpm to have a median (d0.5) droplet size distribution of approximately 10 m. Thus 1 L of W / O emulsion with specific mass of approximately 1.0 g / ml was obtained.
- Table 1 summarizes the parameters (operating conditions) investigated for both US systems.
- Efficiency was calculated by the ratio of water volume separated and the volume of water initially contained in the emulsion, expressed as a percentage.
- each 20 g volume of emulsion subjected to the process contained about 10 mL of emulsified saline. .
- the separation of 4 ml of aqueous phase from 20 g of emulsion corresponds to a separation efficiency of 40%.
- FIG. 2 A system for batching the US is shown in Figure 2.
- the US is applied to a main compartment (9) containing a fluid (10) into which a secondary compartment is inserted.
- transducers electrical energy (13), received from appropriate electronic equipment (such as a signal generator, driver, or source), is supplied to devices called transducers (14), which convert it to mechanical energy in the form of ultrasonic vibration. .
- the vial containing 20 g of emulsion was positioned in the center of the equipment cavity.
- Table 2 shows for each experiment the operating conditions employed and the volume of aqueous phase (saline) separated from the original synthetic emulsion.
- the separation efficiency was calculated by the simple relationship between the volume of the separated aqueous phase and the volume of aqueous phase originally contained in the emulsion (10 ml).
- the demulsification efficiency increases by about 10 percentage points, as efficiency values of 70% and 80% were obtained for 30-minute and 45-minute treatment times, respectively.
- cup horn Systems known as "cup horn” can be considered as an adaptation of conventional US probes. However, the main difference here is that the probe, instead of being immersed in the sample, is positioned at the bottom of a cylindrical container and has a shape that allows a higher concentration of ultrasonic energy, which is transferred to the fluid. contained in the container.
- liquid substances such as saline or mineral oil, may also be used as US propagation media from the base of the cup horn container to the emulsion-containing vial.
- This equipment allows to monitor the amount of ultrasonic energy actually applied to the cylindrical container of the equipment throughout the treatment, and this data is also informed in Table 3.
- A refers to amplitude - percent of maximum power
- t refers to exposure time
- T refers to temperature
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
Abstract
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112014030476A BR112014030476A2 (pt) | 2012-07-09 | 2012-07-09 | processo para a separação de fases de emulsões do tipo água-emóleo por aplicação indireta de ultrassom |
PCT/BR2012/000235 WO2014008559A1 (pt) | 2012-07-09 | 2012-07-09 | Processo para a separação de fases de emulsões do tipo água-em-óleo por aplicação indirecta de ultrassom |
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PCT/BR2012/000235 WO2014008559A1 (pt) | 2012-07-09 | 2012-07-09 | Processo para a separação de fases de emulsões do tipo água-em-óleo por aplicação indirecta de ultrassom |
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WO2014008559A1 true WO2014008559A1 (pt) | 2014-01-16 |
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PCT/BR2012/000235 WO2014008559A1 (pt) | 2012-07-09 | 2012-07-09 | Processo para a separação de fases de emulsões do tipo água-em-óleo por aplicação indirecta de ultrassom |
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BR (1) | BR112014030476A2 (pt) |
WO (1) | WO2014008559A1 (pt) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108554001A (zh) * | 2018-07-03 | 2018-09-21 | 重庆工商大学 | 一种带超声波破乳与静电聚合的聚结滤油机 |
WO2021151183A1 (pt) * | 2020-01-30 | 2021-08-05 | Petróleo Brasileiro S.A. - Petrobras | Uso de nanofluido para remoção de petróleo e sais em amostras de rochas de sistemas petrolíferos |
CN113694855A (zh) * | 2021-10-27 | 2021-11-26 | 胜利油田东强机电设备制造有限公司 | 一种自洁式石油含水电脱水仪 |
WO2022015993A1 (en) * | 2020-07-17 | 2022-01-20 | AWE Technologies, LLC | Hybrid acoustic, centrifugal oil/water separation |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US2257997A (en) * | 1940-11-27 | 1941-10-07 | American Cyanamid Co | Breaking petroleum emulsions |
US3200567A (en) * | 1956-09-07 | 1965-08-17 | Black Sivalls & Bryson Inc | System for the sonic treatment of emulsions and for resolving the same into their constituent parts |
US3594314A (en) * | 1969-02-12 | 1971-07-20 | James R Bilhartz | Method of separating oil,water and solids by ultrasonic treatment |
JPH0810509A (ja) * | 1994-06-30 | 1996-01-16 | Mitsubishi Kakoki Kaisha Ltd | 船舶廃油の処理方法 |
ES2299889T3 (es) * | 2003-09-22 | 2008-06-01 | Ingenieurburo Gebr. Seyrich Gmbh | Procedimiento e instalacion para el tratamiento de emulsiones organicas acuosas. |
-
2012
- 2012-07-09 BR BR112014030476A patent/BR112014030476A2/pt not_active Application Discontinuation
- 2012-07-09 WO PCT/BR2012/000235 patent/WO2014008559A1/pt active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US2257997A (en) * | 1940-11-27 | 1941-10-07 | American Cyanamid Co | Breaking petroleum emulsions |
US3200567A (en) * | 1956-09-07 | 1965-08-17 | Black Sivalls & Bryson Inc | System for the sonic treatment of emulsions and for resolving the same into their constituent parts |
US3594314A (en) * | 1969-02-12 | 1971-07-20 | James R Bilhartz | Method of separating oil,water and solids by ultrasonic treatment |
JPH0810509A (ja) * | 1994-06-30 | 1996-01-16 | Mitsubishi Kakoki Kaisha Ltd | 船舶廃油の処理方法 |
ES2299889T3 (es) * | 2003-09-22 | 2008-06-01 | Ingenieurburo Gebr. Seyrich Gmbh | Procedimiento e instalacion para el tratamiento de emulsiones organicas acuosas. |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108554001A (zh) * | 2018-07-03 | 2018-09-21 | 重庆工商大学 | 一种带超声波破乳与静电聚合的聚结滤油机 |
WO2021151183A1 (pt) * | 2020-01-30 | 2021-08-05 | Petróleo Brasileiro S.A. - Petrobras | Uso de nanofluido para remoção de petróleo e sais em amostras de rochas de sistemas petrolíferos |
CN115917117A (zh) * | 2020-01-30 | 2023-04-04 | 巴西石油公司 | 纳米流体用于去除来自石油系统的岩石样品中的石油和盐的用途 |
US12188854B2 (en) | 2020-01-30 | 2025-01-07 | Petróleo Brasileiro S.A.—Petrobras | Use of nanofluid to remove oil and salts from rock samples in petroleum systems |
WO2022015993A1 (en) * | 2020-07-17 | 2022-01-20 | AWE Technologies, LLC | Hybrid acoustic, centrifugal oil/water separation |
CN113694855A (zh) * | 2021-10-27 | 2021-11-26 | 胜利油田东强机电设备制造有限公司 | 一种自洁式石油含水电脱水仪 |
CN113694855B (zh) * | 2021-10-27 | 2022-02-18 | 胜利油田东强机电设备制造有限公司 | 一种自洁式石油含水电脱水仪 |
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Publication number | Publication date |
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BR112014030476A2 (pt) | 2017-09-12 |
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