Patent Application
20220152528
The present invention is directed to a method for the treatment at least one emulsion by applying at least one time dependent electrical field and a device for carrying out the method.
A liquid/liquid dispersion and especially an emulsion is a mixture of 2 or more liquids that are normally immiscible, such as oil and water. One of the liquids (inner phase) is dispersed in the other liquid (outer or continuous phase) in form of fine droplets. Thereby emulsions show the smallest sized distributed droplets. In general, also emulsions are thermodynamically instable, whereby due to the free enthalpy (AG equals negative) the small droplets coalesce to larger droplets. Due to gravity the two phases finally separate. Nevertheless emulsion are temporary thermodynamically stable and thus the break-up, coalescence and settling of the droplets need an appropriate time. Thus, well known separation apparatuses are huge and bulky.
In many chemical processes, efficient removal of a dispersed water phase from a continuous oil phase is highly desirable. Several commercially available methods are described in the professional literature (EOW, J. S.; GHADIRI, M.: Electrostatic enhancement of coalescence of water droplets in oil: a review of the technology; Chem. Eng. Journal, pp. 357-368, No. 85, 2002).
Commercially available methods can be roughly categorized in
The methods differ in their applied physical/chemical principles of operation, such as influencing the
Each of the first four classified methods plus the electrocoagulation has its own advantages and disadvantages, e.g. chemical demulsifiers can advantageously modify the water/oil interfacial properties, thus allowing water droplets to coalesce more easily into larger droplets. However additional problems are encountered in the removal of the agents from the separated aqueous and/or oil phases. pH-Adjustment works sometimes efficient when separating Oil-in-Water (O/W)-emulsions, however fails principally in case of Water-in-Oil (W/O)-emulsions. Latter emulsion-type (W/O-emulsion) is main object of the present invention. Centrifugation is related to high operation costs (mechanical acceleration, material and apparatus strength, maintenance). Heat treatment can reduce the viscosity of the oil, thus allowing any water droplet to fall more rapidly through the oil phase and further advantageously helps in the separation of any entrained gas in the gained crude oil for example. However, heat, physical, mechanical and chemical treatment is rather expensive, and heating has furthermore a tendency to result in high fuel consumption.
Thus, the object of the present invention was now to overcome the disadvantages of the presently applied methods, in particular to provide a method for separating emulsions in an energy and cost efficient manner providing a high degree of separation in short residence times. Electro-coagulation, wherein an electrode serves as a chemical reactant, is not part of the present invention.
According to the invention at least one time varying or temporal changeable electrical field is applied to the emulsion to be treated or broken up. Time varying fields in this context are Alternating Current (AC)-fields or Pulsed Direct-Current (DC)-fields. The invention is concerned on the high-efficient break-up of Liquid/Liquid (L/L)-emulsions of the (W/O)-type and the practically complete separation (>95%) of the formed heavy and light phase in the same splitting module (apparatus) in less than 5 [min].
The application of a time varying electrical field has multiple advantages. These are the design of less mechanical strength apparatuses/machines, the complete elimination of chemicals such as de-emulsifiers and/or flocculants and auxiliary agents. Thus, electrical emulsion separation is both most effective and extremely cost-beneficial.
The present methods described allow a separation of the emulsion in a light and a heavy phase with a de-emulsification rate of at least 95%, preferably more than 97% and particular preferably of more than 99% within a short time period or residence time.
It is also to be understood that the treated emulsion is a dispersion of a polar liquid phase (often the heavy phase) in a non-polar liquid phase (often the light phase)—L/L-emulsion such as Water in Oil.
The de-emulsification rate is per definition:
The Electrical Field Strength E is per definition:
According to a first variant of the invention a method for the separation of least one emulsion by applying at least one time varying or temporal changeable electrical field is provided, wherein the at least one electrical field is a singular high frequency (HF) alternating current (AC) field with an electrical field strength E between 2,000 and 100,000 V/m and a high frequency (HF) between >10,000 Hz and 200,000 Hz.
Within the meaning of the present invention the expression High frequency (HF) means frequencies of more than 1,000 [Hz] and the expression Low frequency (LF) means frequencies lower than 1,000 [Hz] and especially the electrical net frequencies of 50/60 Hz in Europe/USA.
In an embodiment of the present method the at least one HF/AC-field is applied with an electrical field strength between 2,000 and 100,000 V/m and a high frequency between 12,000 and 150,000 Hz, preferably between 15,000 and 100,000 Hz, in particular preferably between 20,000 and 70,000 Hz, most preferably between 25,000 and 50,000 Hz.
Only the combination of the electrical parameters of a high electrical field strength (E) and a high frequency (HF) allows for a complete break-up of the emulsion and complete separation of the light and heavy phases in only one apparatus within less than 5 min.
In the most preferred embodiment the HF/AC field is applied with a field strength between 4,000 and 70,000 V/m, preferably between 30,000 V/m and 50,000 V/m and a frequency between 12,000 and 150,000 Hz, preferably between 15,000 Hz and 100,000 Hz, in particular between 20,000 Hz and 70,000 Hz and most preferably between 25,000 and 50,000 Hz. For example, in one variant a HF/AC field has an electrical field strength between 30,000 and 50,000 V/m and a high frequency between 16,000 and 40,000 Hz.
According to a second variant of the present invention a method for the separation of at least one emulsion by applying at least one direct current (DC) field and an at least one alternating current (AC field) is provided, wherein the at least DC field and the at least one AC field are applied in series to the emulsion to be treated. In this second variant the at least one alternating current (AC) field is applied with an electrical field strength between 2,000 and 100,000 V/m and a frequency (HF) between 1,000 Hz and 200,000 Hz.
Thus, in this case a method for separating emulsions such as water-in-oil (W/O)-emulsions is described which applies a combination of electrical fields whereby the emulsified phase is separated in a view minutes completely in its singular phases. This method differs from the known emulsion separation methods using electrical fields in a serial arrangement and/or serial application of the different fields, especially by the application of an HF/AC-field in combination with a DC-field.
The present methods described allow a separation of the emulsion in a light and a heavy phase with a de-emulsification rate of at least 95%, preferably more than 97% and particular preferably of more than 99% within a short time period or residence time. The residence time may be less than 5 min, preferably less than 3 min, in particular preferably less than 2 min.
Only the serial combination of especially an upwards orientated DC-field with a downstream orientated HF/AC-field are particularly advantageously and allow a complete (ηseparation>99%) break-up of the emulsion and separation of the light and heavy phases in only one apparatus (module) within less than 3 min.
In case of an upstream DC field a pre-orientation and a movement/approach of the polar water molecules and/or polar components of the emulsion are affected as described in detail further below.
In an embodiment of the combined fields up to 10 DC and HF/AC fields are applied in series to the emulsion in an alternating manner. In a further embodiment the at least one DC field and the at least one HF/AC field are applied to the emulsion in the serial order DC field followed by HF/AC field.
Different combinations of DC and HF/AC fields are thereby possible. Thus, in one embodiment at least one non-pulsed or steady direct current (DC) field and at least one high frequency (HF) alternating current (AC) field is provided, wherein the at least one DC field and the at least one HF/AC field are applied in series to the emulsion to be treated.
In another embodiment at least one pulsed DC field and at least one HF/AC field are applied in series to the emulsion to be treated.
In a yet further preferred embodiment of the present method the at least one DC field and the at least one AC field are applied to the emulsion in the serial order DC field followed by HF/AC field, i.e. the DC field is arranged or applied to the emulsion upstream of the HF/AC field.
In another preferred embodiment is also possible to apply the at least one HF/AC field to the emulsion in the serial order HF/AC field followed by DC-field, i.e. the at least one HF/AC field is arranged or applied upstream of the DC field.
It is also possible and conceivable to apply at least one DC field and at least two AC fields to the emulsion. In such a case the at least one DC field and the at least two AC fields are applied to the emulsion in the serial order first HF/AC field followed by DC field followed by HF/AC field. In other words, the at least first HF/AC field is applied upstream of the DC field and the at least one second HF/AC field is applied downstream of the DC field.
In case of an upstream DC field a pre-orientation and a movement/approach of the polar water molecules and/or polar components of the emulsion are affected as described in detail further below.
Amongst the above described possible arrangements and order of application of DC and HF/AC fields the following combinations are the most preferred:
Within the meaning of the present invention “upstream” means that the respective first field is arranged or applied in front of the respective second field; e.g. steady DC-field in front of or before HF/AC-field.
The field strength of the at least one HF/AC field applied to the emulsion in the combined method is in the range between 2,000 and 100,000 V/m, preferably between 4,000 and 70,000 V/m, most preferably between 30,000 V/m and 50,000 V/m.
The frequency of the HF/AC field is between 1,000 and 200,000 Hz, preferably between 5,000 and 150,000, more preferably between 10,000 and 100,000 Hz, in particular preferably between 20,000 and 70,000 Hz, most preferably between 25,000 and 50,000 Hz.
The field strength of the at least one steady DC field applied to the emulsion in the combined method is in the range between 500 and 20,000 V/m, preferably between 1,000 and 10,000 V/m.
The field strength of the at least one pulsed DC field applied to the emulsion in the combined method is in the range between 500 and 20,000 V/m, preferably between 1.000 and 10,000 V/m and the frequency is between 1 and 1,000 Hz, preferably between 5 and 500 Hz, more preferably between 10 and 250 Hz, most preferably between 10 and 100 Hz. The combination of an electrical filed strength between 1,000 and 10,000 V/m and a frequency between 10 and 100 Hz is mostly preferred.
In another preferred embodiment of the present combined method the electrical power input of the at least one DC field applied to the emulsion is smaller than the electrical power input of the at least one HF/AC field applied to the emulsion. In other words the DC electrical power ratio is smaller than the electrical power HF/AC fraction. For example the at least one DC field can be applied with a power percentage of 5 to 50%, preferably 10 to 40%, most preferably 20 to 30% in respect to the overall applied electrical field (100%). This means in turn, that the percentage of the HF/AC-field applied is 50 to 95%, preferably 60 to 90%, most preferably 70 to 80%.
According to the preferred embodiment of a serial combination of first DC-field followed by HF/AC-field it was shown, that the specific energy input for the complete break-up and settling of a phenolic emulsion could be lowered from 10.8 Wh/kg (singular HF/AC-field) to 0.9 Wh/kg (singular DC-field) to minimal 0.36 Wh/kg (combined DC-HF/AC-field), whereby the phenolic emulsion with a water content of 25 wt. % was separated within less than 2 min.
The emulsion to be separated is a Water-in-Oil (0/W) emulsion or multiple Oil-Water-Oil (O/W/O) emulsion. Thus, the present methods are directed to the enhanced break-up of following systems: in general liquid/liquid dispersions, emulsions or multiple emulsions, especially Water-in-Oil emulsions [(W/O)-emulsions] or multiple emulsions of the (O/W/O)-emulsion type and especially to emulsions with water contents up to 70 wt %, preferably of more than 10 wt % up to 70 wt % and most preferably of more than 20 wt % up to 70 wt %.
Generally, (W/O)-emulsions are readily formed in by mixing water in oil phases in a lot of chemical and especially petrochemical processes, such as wash and neutralization operations (caustic tower wash after crack-processes, neutralization wash after chemical reaction) or by separating inorganic components such as salts by contacting an oil phase with an aqueous phase (e.g. catalyst wash) or during the production of e.g. crude oils. Latter (W/O)-emulsions show typically water contents of less than 20 wt %−in average ca. 3 wt %. (W/O)-emulsions causing problems at different stages of the production such as corrosion of pipes, pumps and other processing equipment, complications due to increased emulsion viscosity (finely dispersed small water droplets), deactivation of catalysts (hydrolysis, poisoning) in the presence of water, increased transport costs, because of included water phase and finally increased operation costs by additional post-treatment plants (e.g. waste water treatment).
Thus, there are a number of commercial reasons for removing this emulsified water from organic phases. In particular, electrical emulsion separation is both most effective and extremely cost-beneficial. The unique disadvantage of electrical splitting of emulsions can be found in their known applicability on preferable (W/O)-emulsions and not on the more often (O/W)-emulsions.
The state of the art in electrical treatment of (W/O)-emulsions has been predominately defined in crude oil production and petrochemical processes. Typical crude-oil desalination plants operate preferably with Alternating Current (AC)-fields at net (low) frequencies (50/60 Hz), and to a lesser extent, Direct Current (DC)-fields are used for the separation of water droplets from crude oil (danger on short-circuiting and electrolysis phenomena especially by the usage of bare metal electrodes). Thereby, the conventional electro-separators are huge, as large residence times are required for the electro-coalescence regions and settling zones to separate the enlarged water droplets from the crude oil.
Nevertheless, only timely varying electrical fields such as AC- or a serial combination of AC- and DC-fields (as applied in the present methods) can influence the strength of the stabilizing film by induced vibration of the relevant electrostatic double layer. The effect lead to a weakness of the electrostatic stabilizing film (surrounding the droplet), which is also the relevant energy barrier. This energy barrier of the droplets can only be influenced by timely changing electrical field methods, because the stabilizing electrostatic double layer (ξ-potential) is particularly influenced by the frequency of the applied electrical field.
In DRAXLER, J.; MARR, R. (Auslegungskriterien für elektrostatische Emulsionsspaltanlagen; Chem.-Ing.-Tech., 62, pp. 525-530, No. 7, 1990) it is reported, that the implementation of the Liquid-Membrane-Permeation (LMP) process lead to remarkable progresses in the field of electrical splitting of (W/O)-emulsions. The emulsions in the LMP-process are deliberate synthetically stabilized (necessary life time during mass transfer operation/apparatus) and following are more stable than crude-oil emulsions. The (W/O)-emulsions in the LMP-process are characterized by extreme small sized water droplets, narrow droplet size distributions and a higher content of water in comparison to typically crude-oil-emulsions. Thus, the well-known electrical methods for emulsion splitting (crude oil emulsion electrical splitting) are extremely inefficient for these special types of (W/O)-emulsions. Thus, in Draxler et al. both High Voltage (HV) and High Frequency (HF) Alternating Current (AC)-fields are recommended for an enhanced separation and efficient enough emulsion separation rate of such synthetically stabilized (W/O)-emulsions.
Furthermore, Draxler et al. describe an existing correlation between maximal allowed voltage and frequency of the applied AC-field. Herein, the re-emulsification starts not as a function of applied maximal voltage alone, but rather by increasing the frequency of the applied AC-field to a maximal tolerable value. For example: Re-emulsification takes initially place at 3.000 V and by frequencies higher than 10,000 Hz. Frequencies lower than 5,000 Hz show maximal de-emulsification rate ηseparation of at best 70% by application of 3.000 V, maximal 55% by 1.000 V and less than 10% by 220 V. Nevertheless, that means that the break-up and separation of the light and heavy phase is despite the application of a HF/AC-field not complete, because of both missing de-emulsification efficiency or re-emulsification effects.
A further development of the HV-HF/AC-technology is described in SWATEK, H.; ORTMAYR, E.; Chem.-Ing.-Tech., 64, pp. 803-804, No. 9, 1992. Here a DC-field is overlaid (parallel) to a HF/AC-field. The DC-field is introduced by the usage of a kind parallel plate capacitor, which is overlaid with an HF/AC-field (sinus-wave). The DC-field should effect an additional positive polarisation of the water molecules. The parallel combined HF/AC-/DC-field should enhance the separation of fine dispersed water droplets of (W/O)-emulsions.
The correlation between an optimal frequency and an enhanced electro-coalescence of water droplets is not fully understood until today. Nevertheless, the magnitude of the applied frequency depends greatly on the type of electric field, as well as on the arrangement of the electrodes. In BRAUN, A. H.; HANSON, C.: Effect of oscillating electric field on coalescence in liquid-liquid systems; Trans. Faraday Soc., 61, p. 1754, 1965 is initially reported, that an optimum frequency could be observed at which coalescence occurs more efficient. More recently, the existence of an optimum frequency has also reported in BAILES, P. J.: Pulsed d.c. fields for electrostatic coalescence of water-in-oil emulsions; Trans. IChemE A, 73, pp. 559-566, 1995, whereby the adjustment of an optimal frequency is especially important at low applied potentials (DC-fields). It is reported, that in this case the insulation material and its thickness of the electrode beside the liquid composition of the emulsion are the main influencing parameters for the optimal frequency. Generally, low frequencies are usually used with pulsed DC-electrical fields. BAILES, P. J.; LARKAI, S. K. L.: Electrostatic separation of liquid dispersions; UK-Patent 2.171.031 A, 1986 applied a pulsed DC-field at a frequency less than 1 Hz. BAILES, P. J.; WATSON M.: Electrostatic and centrifugal separation of liquid dispersion; UK-Patent 2.249.741 A, 1992 used a pulse rate of 25 Hz in a rotating cylindrical coalescer, whilst in BAILES, P. J.: Resolution of emulsions; U.S. Pat. No. 5,580,464, 1996 the optimal frequency was found at 15 Hz.
(W/O)-Emulsions are especially characterized by smallest sized distributed water droplets in an oil phase (liquid/liquid-dispersion), whereby beside the movement of the droplets to each other especially the coalescence requires the overcoming of an energy barrier (comparable to a kind of activation energy). The whole mechanism of droplet-coalescence can be structured into 3 sub-steps: movement and approximation of the water droplets to each other by e.g. gravity, centrifugal or electrical forces; drain off the film between the droplets and break-up of the film and coalescence of droplets and the boundary layer (film).
The available separation technologies are primary concerned on the 1st sub-step (movement and approximation), whereby the drain-off and the break-up of the protecting (stabilizing) film are only defined by the material properties (interfacial tension, energy barrier).
Also, the electrical caused emulsion break-up and coalescence is especially characterized by an initially increased movement and approximation of the water-droplets to each other (1st sub-step). This is similar to the other different separation technologies, whereby in the latter mentioned separation technologies only the movement and approximation of the water droplets can be supported. By the usage of electrical fields also the break-up of the film (3rd sub-step)—not the drain off the film (2nd sub-step)—can be advantageously influenced by timely varying or temporal changeable electrical fields.
All electrical analytical models show (dipole-dipole interference, electrophoresis, di-electrophoresis), that the resulting electrical force Felectric on the water droplet is a function of 2nd order of the electrical field strength E applied:
F
electric
=f(E2(t))
The maximal possible electrical field strength E supports the movement of the water droplets to each other. Nevertheless, the maximal tolerable electrical field strength E is limited by the danger of short-circuits; break down of the electrical field itself and the appearance of re-emulsification effects. Similar, the 2nd sup-step of the whole coalescence mechanism, the drain-off the film cannot be influenced—also not by the application of electrical fields. However, the 3rd sub step of the whole mechanism the break-up of the film is supported by electrical fields, what can be also macroscopic observed, especially by the application of high frequencies in AC-fields. The pulsation of the electrical field supports the break-up of the film between two droplets.
Timely varying electrical fields such as AC- or pulsed DC-fields can at least influence the strength of the stabilizing film by induced vibration of the relevant electrostatic double layer and their “bounded” water-molecule cluster-structures. The effect lead to a weakening of the electrostatic stabilizing film (surrounding the droplet), which is also the relevant energy barrier. This energy barrier of the droplets can only be influenced by changing or timely modifiable electrical field methods, because the stabilizing electrostatic double layer (ξ-potential) is particularly influenced by the frequency of the applied varying electrical field.
The present methods according to the invention allow an enhanced break-up of liquid/liquid-dispersions and especially emulsions under impact of singular and combined electrical fields by an optimized process parameter adjustment, optimized design of electro-separator and finally combination of electrical fields therein, especially regarding the enhanced break-up of a Phenol containing emulsion, independently on the emulsion type, preferably on the break-up of (W/O)-emulsions and most preferably on emulsions with water contents of more than 20 wt. % up to 70 wt. %.
The emulsion splitting or treating method of the present invention allow an enhanced break-up of following systems: in general liquid/liquid-dispersions, emulsions or multiple emulsions, especially water in oil emulsions [(W/O)-emulsions] or multiple emulsions of the (O/W/O)-emulsion type, particularly emulsions with water contents up to 70 wt. %, preferably of more than 10 wt. % up to 70 wt. % and most preferably of more than 20 wt. % up to 70 wt. % and quite particularly (W/O)-emulsions from a petrochemical process like emulsions from phenol synthesis (cleavage wash, Hock synthesis); washing procedures (e.g. catalyst wash, caustic or alkaline wash, BTX-wash operations, atmospheric and vacuum distillation fractions to wash towers); cooling procedures (e.g. quench wash tower) and/or crude oil desalting steps. In a most preferred embodiment the emulsion to be separated is a phenolic water emulsion of the Hock-synthesis with an equimolar Phenol/Acetone-ratio and water contents up to 70 wt. %, especially 20 to 70 wt. % and most preferably of 25 wt. %.
As described above the serial combination of an upstream orientated DC-field followed by a downstream orientated High Frequency—HF/AC-field is a preferable embodiment of the present method. The upstream orientated DC-field causes initially the polarization of the water molecules and thus an enhanced movement of the water droplets (dipoles) to each other (1st sub-step of coalescence; movement and approximation) by increased/optimized electrical field strength. This movement and approximation of water droplets can also be macroscopic observed by the formation of pre-orientated or better coordinated water molecule clusters, the so-called string of pearls formation (transparent appearance of the heavy (aqueous) phase).
In the downstream orientated High Frequency HF-/AC-field an enhanced coalescence of the water droplets to finally an associated aqueous bulk phase can be macroscopic observed. The downstream orientated HF/AC-field, especially operated at high frequencies, can interact with the pre-orientated and nearby orientated water molecule clusters resulting from the pre-orientated DC-field. The electrostatic protective layer is not able to follow high frequent polarity changes of an HF/AC field, while water droplets at least partially take up high frequent vibrations, supporting especially the break-up of the film (3rd sub-step of coalescence). The downstream orientated HF/AC-field can at least influence the strength of the stabilizing film by induced vibration of the relevant electrostatic double layer and their “bounded” water-molecule cluster-structures. The water molecule clusters are at lowest distance as possible, because of the pre-orientated DC-field. The High Frequency effect lead quickly to a weakening of the electrostatic stabilizing film (surrounding the droplet), which is also the relevant energy barrier. This electrostatic stabilizing layer is both weakened and not able to follow the high frequent polarity changes of the HF/AC-field, while the water droplet clusters are able to follow the high frequent oscillations. Water droplet clusters take up high frequent vibrations, affecting especially the break-up of the stabilizing film. A coalesced aqueous phase is formed promptly. Furthermore, the specific energy consumption for the break-up of the emulsion can be reduced significantly to a minimum by the serial combination of a 1st-DC- with a 2nd-HF/AC-field, remarkable in comparison to singular AC- or DC-fields.
In case of the most preferred embodiment of the method for separating the emulsion, which is a combination of DC field with an HF/AC-field wherein the DC field is upstream of the high frequent HF/AC field, the emulsion is introduced at first via the DC field. Thereby the polar components moved towards each other, the dipoles of the polar components (for instance emulsified water droplets) align and orient themselves to a coordinated phase. A coalescence of the emulsion droplets into a heavier and a lighter unified phase already takes place partially in the DC field.
In one preferred embodiment of the present method the complete separation of polar (water) and less polar (nonpolar) phases of the emulsion phase takes place in only a few minutes. The required separation time can be less than 5 min, preferably less than 3 min, in particular preferably less than 2 min.
It also has been shown that a doubling of the frequency at the same voltage amplitude can effect a halving of the separation time. Due to the higher coalescence efficiency when using high frequency fields there is the possibility to obtain high flow rates in small separation volumes, while the presently known coalescence systems often require bulky device volumes. Opposite to the results of Draxler et al. a re-emulsification was not noted by the electrical splitting of a phenolic emulsion in a HF/AC-field of the present invention.
The extremely short de-emulsification times are advantageously in the dimensioning of the separation device, i.e. in case of a short de-emulsification time it is sufficient to provide a device with small volume. Thus, a complete break-up of the emulsion and complete separation of the light and heavy phases in only one apparatus within less than 5 min can be realized.
The present methods are conducted in a device for separating or treating at least one emulsion comprising the following features:
The vessel may also be described as a combination of several modules each comprising the electrodes. Thus, the individual (electro-coalescence) modules (for example up to 10 modules) can be combined to an electrical separator/decanter vessel, preferably in a cylindrical horizontal separator/decanter vessel.
In a preferred embodiment of the present device at least one further third electrode is positioned alongside the at least one module of the vessel, in particular alongside the inner or outer circumference of the at least one module of the vessel.
In a yet other preferred embodiment of the present device the at least one module of the vessel is separated into at least two sections, preferably into at least three sections. In this case at least one HF/AC-field is applied to at least one section and at least one DC field is applied to the at least other section.
In case of three sections there is a combination of a HF/AC-field applied in the first section and third section by combining electrodes positioned along the walls of the vessel or module and the central positioned electrode in the vessel or module interior. The DC field can be applied in the second middle section by a third electrode combined with the central positioned electrode. All three sections are insulated against each other by an appropriate sealing such as PTFE, sealing.
In all variants of the present device the HF/AC-field is generated between the electrodes by at least one HF/AC-field generator and the DC-field is generated by at least one DC-field generator.
The present device can also be described with the following features:
Furthermore the presently used electro-coalescence module is separated into at least two sections. Thereby the at least one cylindrical electrode for applying at least on DC-field is used to divide the electro-coalescence module into said sections. This can be done by positioning the DC-field at any predetermined position alongside the electro-coalescence module, preferably in front of the HF/AC-field.
The at least one electrode positioned in the center of the vessel is preferably arranged along the symmetrical axis of a cylindrical electro-coalescence module and is preferably designed at a rod shaped electrode used for grounding.
The specific arrangement of the electrodes and the division of the electro-coalescence module in multiple sections enables that at least one HF/AC-field can be applied to at least one section and at the least one DC-field is applied to the at least other section.
This can be done such that the at least one DC-section is applied or arranged upstream of the at least one HF/AC-section or the at least one HF/AC-section is applied upstream of the at least one DC-section. Furthermore, it is also possible to use three sections whereby at least two HF/AC-sections and one DC-section are provided such that at least one first HF/AC-section is upstream of the at least one DC-section and the at least one second HF/AC-section is downstream of the at least one DC-section.
The present invention is subsequently described with reference to the figures of the drawings by means of multiple examples. It shows:
In batch operation the inner volume of the lab glass tube separator is filled initially with the emulsion phase and following the electrical field is applied. In continuous operation, the (W/O)-emulsion is fed in the lower section of the lab glass tube separator. The emulsion is separated into a light and heavy phase by application of an electrical field. The light (organic) phase emerges the glass tube separator on the top, whereby the heavy (water) phase is discharged on the bottom of the glass tube separator. The level of the heavy phase in the decanter separator is controlled by a syphon.
In continuous operation, the emulsion phase is fed with a peristaltic pump from the emulsion feed tank to the central orientated inlet tube of the horizontal glass decanter separator. The emulsion phase is separated into a light and heavy phase by application of an electrical field over the length of the horizontal glass decanter separator. The light (organic) phase emerges the horizontal glass decanter separator on the top, whereby the heavy (water) phase is discharged on the bottom of the horizontal decanter separator. The level of the heavy phase in the decanter separator is controlled by a syphon.
In
In continuous operation, the emulsion phase is fed with a peristaltic pump from the emulsion feed tank to the central orientated inlet tube of the 3Z-horizontal glass decanter separator. The emulsion phase is separated into a light and heavy phase by application of electrical fields in combination over the length of the 3Z-horizontal glass decanter separator. The light (organic) phase emerges the 3Z-horizontal glass decanter separator on the top, whereby the heavy (water) phase is discharged on the bottom of the horizontal decanter separator. The level of the heavy phase in the decanter separator is controlled by a syphon.
In
In continuous operation, the emulsion phase is fed with a peristaltic pump from the emulsion feed tank to the central orientated inlet tube of the horizontal glass decanter separator. The emulsion is separated into a light and a heavy phase by application of parallel combined (overlaid) electrical HF/AC-field with a DC-field over the total length of the horizontal glass decanter separator. The light (organic) phase emerges the horizontal glass decanter separator on the top, whereby the heavy (water) phase is discharged on the bottom of the horizontal decanter separator. The level of the heavy phase in the decanter separator is controlled by a syphon.
Definition of Water in Oil (W/O)-Emulsion (Model/Test Emulsion)
The following examples serve to illustrate discontinuous and continuous operation of the electrical emulsion separation according to the invention by means of the model emulsion water/phenol/acetone/cumene-hydroperoxide. That emulsion is obtained in the so called Hock synthesis for producing phenol and acetone, whereby the organic reaction phase is afterwards treated with an aqueous wash phase in the phenol cleavage wash unit operation. Thereby an (W/O)-emulsion is formed.
The investigated Water-in-Oil (W/O)-emulsion has a starting (feed) water-concentration of about 25 wt. %. The main component is Phenol, beside the further relevant components such as acetone, water and cumene-hydroperoxide. The initial composition of the applied phenolic (W/O)-emulsion is the following ones:
The phenolic (W/O)-emulsion in Tab. 1 was used in all experiments as a kind of model emulsion. The preparation of the emulsion is done both freshly and continuously with a rotor/stator mixer (Fa. IKA, Type: ULTRA TURRAX T25)—before electrical splitting experiments were executed.
It has to be mentioned that the—minimal attainable final concentration of water in the separated organic phase is the equilibrium concentration of the material phase system, which is about 10 wt. % and defines thus indirectly the maximal attainable separation performance of the test material phase system. The water content in the light (organic) phase will be analyzed indirectly by Karl Fischer method of the resulting light (organic) phase. Furthermore a continuous analysis of the water content could be performed by density measurements of the separated organic phase online.
Example 1 (comparative example): Batch separation of a phenolic (W/O)-emulsion of Tab.1 by applying a singular AC-field at the net frequency of 50 Hz and at three effective Voltage levels of 150, 250 and 500 V.
The phenolic (W/O)-emulsion of Tab.1 with an initial water content of about 25 wt. % is transferred to the LAB GLASS TUBE SEPARATOR of
The results of experiment 1 in Tab. 2 show impressive, that the phenolic model emulsion of Tab. 1 cannot be broken-up both at especially frequency of 50 Hz and effective Voltages between 150 V and 500 V or more detailed electrical field strengths between 9,000 and 30,000 V/m at low frequencies of 50 Hz—this in difference to the knowledge from crude oil desalination processes. The water contents of the electrical treated organic phases conform practically to the starting water concentration of 25 wt. % of the feed emulsion after 30 min. The achieved results (non-applicability) confirm, that AC-fields at low (net) frequencies cannot break-up phenolic (W/O)-emulsions of composition of Tab. 1, which also indicates the high thermodynamically temporary stability of the phenolic emulsion test system—comparable with synthetically generated emulsions of the Liquid/Membrane/Permeation process. Such (W/O)-emulsions are thermodynamically stable over hours or days under influence of gravity alone.
Example 2: Continuous separation of a phenolic (W/O)-emulsion of Tab.1 in a singular AC field at high frequencies (3,750-32,000 Hz).
Example 2 should demonstrate that very stable (W/O)-emulsions such as the phenolic test emulsion of Tab. 1, could be broken-up also at “low” AC-voltage (electrical field strength E) of 500 V, respectively electrical field strength of app. 16.000 V/m, by application of HF/AC-fields and especially high frequencies between 3,750-32,000 Hz—this in difference to example 1 (500 V/50 Hz), where a LF/AC-field was applied.
The phenolic (W/O)-emulsion of Tab.1 with an initial water content of about 25 wt. % is transferred in the 1Z-horizontal decanter separator (see
The diagram of
The experiments of example 2 show that the phenolic model emulsion of Tab. 1 starts to split in an HF/AC-field (500 V) at 3,750 Hz. The residual water content of the light (organic) phase decreases remarkable by increasing the high frequency from 3,750-32,000 Hz—resp. 21.4 wt % at 3,750 Hz to 13.0 wt % at 32,000 Hz. The equilibrium water concentration of 10 wt % of the test material system cannot be reached with the chosen process parameters—e.g. too short residence time and/or electrical field strength E.
In the experiments (constant average space time) the water content could be reduced from initial 25 wt. % to approximately 13 wt. % at an effective voltage of 500 V and a high frequency of 32,000 Hz. The analytical evaluation of the test series shows a linear function of the resulting water content of the light (organic) phase from the applied high frequency. Furthermore, a disadvantageously re-emulsification was not determined in the chosen process window as it is described in Draxler et al. at 10,000 Hz for synthetically generated LMP-emulsions.
Example 3: Continuous operated enhanced break-up of a phenolic (W/O)-emulsion of Tab.1 in singular DC-fields
The construction of the separation device is the 3Z-horizontal glass decanter separator (subsequently designated as 3Z-decanter separator), which is shown in
The electrical separation is operated continuously. The phenolic model emulsion of Tab.1 with an initial water content of 25 wt % is introduced by means of a peristaltic pump into the 3Z-decanter separator of
A DC-power input of at least 9 W is necessary to guarantee the complete separation (equilibrium water content of 10 wt % of the model emulsion at a continuous mass flow rate of 11.1 kg/h through the 3Z-horizontal decanter separator (=fixed average space time) within less than 2 min. Furthermore,
The obtained results of example 3 show that the phenolic emulsion of Tab. 1 could be completely separated in a DC-field within less than 2 min by applying at least an electrical field strength of more than 7.000 V/m at low specific electrical power input of 0.9 Wh/kg.
Example 4: Continuous operated enhanced break-up of a phenolic (W/O)-emulsion of Tab.1 in singular HF/AC-fields
The experimental used separation device is the 1Z-horizontal glass decanter separator (subsequently designated as 1Z-decanter separator) of
The phenolic (W/O)-emulsion of Tab.1 is continuously transferred via peristaltic pump to the inlet of the 1Z-decanter separator. The phenolic model emulsion of Tab.1 passes the vessel, whereby HF/AC-fields with varying AC-voltages at 16,000 Hz are applied. The experiments were conducted with a constant mass flow rate of the phenolic emulsion of 11.1 kg/h (=fixed space time) at defined electrical HF/AC-voltages at a high frequency of 16,000 Hz. The applied electrical field strengths in this test series are in the range from 10,000 to 50,000 V/m. The resulting outlet (organic light) phases are analyzed on their residual water contents.
An AC-power input of at least 120 W is necessary to guarantee the complete separation (equilibrium water content of 10 wt %) of the model emulsion at a constant mass flow rate of 11.1 kg/h through the 1Z-horizontal decanter separator (=fixed average space time). The obtained results of example 4 show, that the phenolic emulsion of Tab. 1 could be completely separated in a HF/AC-field at 16,000 Hz within less than 2 min by applying at least an electrical field strength of 50,000 V/m at a specific electrical power input of 10.8 Wh/kg. The electrical AC-power input is thus remarkable higher in comparison with the singular DC-field. This is caused by the high capacity of the glass wall tube mass of the apparatus.
Example 4 shows that singular HF/AC-fields can enhance the break-up of (W/O)-emulsions, although the specific electrical power input is higher in comparison to singular DC-fields. The phenolic emulsion can be completely broken up within less than 1.7 min A re-emulsification at 10,000 Hz was not determined, as it is described in Draxler et al. Furthermore, an optimal high frequency was also not determined.
Example 5 (comparative example): Continuous separation of a phenolic (W/O)-emulsion of Tab.1 in parallel combined (overlaid) HF-AC-/DC-fields.
Example 5 should principally demonstrate the knowledge that overlaid HF/AC-/DC-fields (parallel interconnection) should show advantages in the efficiency of separation of (W/O)-emulsions. EP 468 954 A2 describes a low separation degree in case of the usage of singular HF/AC-fields, whereby the alternating or better switching polarity of the water molecules (changed and disadvantageously shapes of dipoles) are the reason for the low separation degree in case of stand-alone HF/AC-fields. Furthermore, EP 468 954 A2 describes the low electrical energy utilization in HF/AC-fields especially for the separation (e.g. parallel warming-up of media phase). No information can be found in EP 468 954 A2 regarding the applied Voltage and/or electrical power of both HF/AC- and overlaid DC-fields.
The experimental applied separation device is shown in
The phenolic (W/O)-emulsion of Tab.1 is continuously transferred via peristaltic pump to the inlet of the 1Z-decanter separator. The model emulsion passes the vessel, whereby following field-combinations were applied:
The experiments were conducted with a constant mass flow rate of the phenolic model emulsion of 11.1 kg/h at defined electrical total power inputs. The resulting outlet phases (organic light phase) were analyzed on their residual water content. The applied electrical field strengths in this test series were in the range from 500 to 50,000 V/m.
Example 6: Continuous separation of a phenolic (W/O)-emulsion of Tab.1 in serial combined DC-HF/AC-fields (upstream; DC; downstream: HF/AC) at a constant total electrical power input of only 5 W.
An upstream orientated DC-field will be serial combined with a downstream positioned HF/AC-field at a high frequency of 16,000 Hz. The experimental applied separation device was the 3Z-decanter separator (
The diagram of
Example 6 shows that a complete break-up and separation of a phenolic (W/O)-emulsion could be done by a serial combination of an upstream DC-field with a downstream orientated HF/AC-field within less than 1.5 min. Furthermore, both the total electrical power input is minimal with 5 W resp. 0.45 Wh/kg at advantageously low electrical field strength in comparison to singular DC-fields or singular HF/AC-fields.
Example 7: Discontinuous separation of phenolic (W/O)-emulsions or (O/W)-emulsions in HF/AC-field with different initial water concentration, especially in the range between 20 and 80 [wt %].
The phenolic (W/O)-emulsion or (O/W)-emulsion with a defined initial water content in the range between 20 and 80 [wt %] is transferred to the LAB GLASS TUBE SEPARATOR of
| Number | Date | Country | Kind |
|---|---|---|---|
| 16153408.6 | Jan 2016 | EP | regional |
This application is a divisional of U.S. patent application Ser. No. 17/140,325 filed on Jan. 4, 2021, which is a divisional of U.S. patent application Ser. No. 16/073,394, filed on Jul. 27, 2018, which is the United States national phase of International Application No. PCT/EP2017/051719 filed Jan. 27, 2017, and claims priority to European Patent Application No. 16153408.6 filed Jan. 29, 2016, the disclosures of which are hereby incorporated by reference in their entireties.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 17140325 | Jan 2021 | US |
| Child | 17530608 | US | |
| Parent | 16073394 | Jul 2018 | US |
| Child | 17140325 | US |
