WO2015184487A1 - Purification d'huiles - Google Patents

Purification d'huiles Download PDF

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Publication number
WO2015184487A1
WO2015184487A1 PCT/AU2015/000331 AU2015000331W WO2015184487A1 WO 2015184487 A1 WO2015184487 A1 WO 2015184487A1 AU 2015000331 W AU2015000331 W AU 2015000331W WO 2015184487 A1 WO2015184487 A1 WO 2015184487A1
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WO
WIPO (PCT)
Prior art keywords
oil
hydrogen
water
phase
basic additive
Prior art date
Application number
PCT/AU2015/000331
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English (en)
Inventor
Mark MCNAMARA
Gordon Chung
Michael Lucas
Samir CHAUDHARY
Indu GUPTA
William Hand
Kieran CHANNON
Original Assignee
Hydrodec Group Plc
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 Hydrodec Group Plc filed Critical Hydrodec Group Plc
Publication of WO2015184487A1 publication Critical patent/WO2015184487A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation

Definitions

  • the invention relates to purification of oils.
  • the contaminant may comprise an acid or a conjugate base thereof, or may comprise a substance which, under the conditions of step b), forms an acid or a conjugate base thereof, wherein the acid or conjugate base is capable of poisoning or fouling the hydrogenation system. It may for example comprise, or be, a phosphorus containing compound. Alternatively or additionally it may comprise, or be, a sulfur containing compound.
  • the basic additive may be capable of inhibiting or preventing the poisoning or fouling of the hydrogenation system by the acid or conjugate base. It may be capable of displacing the acid or conjugate base from the catalyst. It may be a stronger base than the conjugate base of the acid, or of the contaminant.
  • the basic additive may be present in step a) in sufficient quantity to ensure at least about 90% removal of the contaminant, optionally at least about 99% thereof.
  • the molar flow rate of the basic additive may be about the same as the molar flow rate of the contaminant or may be greater than the molar flow rate of the contaminant. It may be sufficient to prevent or to substantially prevent fouling of the catalyst.
  • the method may additionally comprise passing the product mixture through a cross- exchanger which heats the oil and the hydrogen, and optionally also the aqueous solution of basic additive, prior to step b).
  • the liquid phase from the separating step may be cooled.
  • An aqueous stream may subsequently be separated therefrom.
  • the product mixture may be degassed prior to separating the aqueous stream therefrom.
  • the degassing may comprise a vacuum degassing step. It may also comprise a step of degassing at or above ambient pressure prior to the vacuum degassing step.
  • the degassed stream may be combined with water prior to separating the aqueous stream from the cooled liquid phase. Thus the degassed stream may be washed with water so as to remove water soluble contaminants.
  • the invention also encompasses an oil produced by the method described above.
  • Fi gure 1 shows a diagrammatic representation of one embodiment of the method of the present invention.
  • Hydrogen unless otherwise stated, this refers to elemental, or molecular, hydrogen (H 2 ). It is commonly either in a gaseous state or in solution or both.
  • a solution of a basic additive which is a base.
  • This solution may optionally have undissolved basic additive (or other undissolved materials) present.
  • a solution containing dissolved basic additive and undissolved (e.g. suspended) basic additive would be within the scope of the term "solution of a basic additive”.
  • basic additive refers to an intentionally added component of the method.
  • conjugate base is used to refer to the conjugate base of an acid where the acid or the conjugate base is a contaminant that is present in the oil as it enters the method or which is generated from such a contaminant.
  • Critical point the temperature and pressure for a particular substance (in the present specification water unless otherwise specified) at which an increase in either temperature or pressure results in the substance existing in a supercritical phase which is neither liquid nor vapour.
  • the temperature at the critical point is referred to herein as the critical temperature and the pressure at the critical point is referred to herein as the critical pressure.
  • Conjugate base the product of removing a proton from an acid.
  • the conjugate base of acetic acid is acetate ion.
  • Partially condensed vapour a fine dispersion of liquid droplets in a gas or vapour.
  • the partially condensed vapour may be a mist or a fog.
  • the droplets may have a number average or volume average diameter of less than about 100 microns, or less than about 50, 20, 10, 5, 2 or 1 micron. They may have a number average or volume average diameter of about 1 to about 100 microns, or about 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 10 to 100, 50 to 100, 5 to 50, 5 to 20, 10 to 50, 10 to 20 or 20 to 50 microns, e.g. about 1 , 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90 or 100 microns.
  • Multiphase consisting of more than one physical phase. Commonly this term will refer to a system in which there are more than one liquid phase, e.g. a water phase and an oil phase which is immiscible with the water phase. In some cases it may refer to a system in which two different types of phase coexist, e.g. one or more gas phases and one or more liquid phases. It may also refer to a system in which more than one physical phase coexists, e.g. solid, liquid and gas.
  • a bulk liquid water phase there will commonly be a bulk liquid water phase, a bulk liquid oil phase, a partially condensed water vapour phase, possibly a partially condensed oil vapour phase and a water vapour phase, as well as a solid catalyst phase.
  • Aqueous containing water and being largely miscible with water.
  • An aqueous liquid may be at least 50% water on a weight basis, or at least about 60, 70, 80, 90, 95 or 99% water.
  • An aspect of the present invention is that it allows for reduction, optionally prevention, of fouling or poisoning of a catalyst, a catalyst bed, a catalytic reactor or a catalytic reactor system during catalyzed hydrogenation of a feed oil contaminated by compounds capable of undergoing poisoning or fouling processes or reactions within the reactor system, while also reducing the concentration of a contaminant in the feed oil.
  • the present method reduces at l east one of these contaminants, and may optionally reduce more than one, optionally all, of the contaminants. The reduction in this case is relative to the fouling or poisoning, or of the concentration of the contaminants using conventional hydrogenation methods.
  • the contaminants discussed above may be present in the oil prior to entering the method at a level of hundreds or even thousands of ppm on a weight/volume basis or a weight/weight basis. They may be present at up to about lOOOOppm, or up to 5000, 2000 or lOOOppm.
  • the hydrogenation reaction is commonly conducted in a hydrogenation reactor.
  • feed oil and/or one or more reagents may be preheated before they are fed to the reactor. They may be preheated to a temperature at or near the desired reaction temperature (described elsewhere herein).
  • a recycled hydrogen stream is combined with the feed oil and the resulting stream is mixed with an aqueous solution containing the basic additive (such that the molar flow of the basic additive may be equal to or greater than the molar flow of the contaminant). This is then heated using a heat exchanger and optionally also a cross exchanger, to about the desired reaction temperature.
  • the combined hydrogen and feed oil is heated using a heat exchanger and optionally also a cross exchanger, to about the desired reaction temperature and the aqueous solution containing the basic additive is then added.
  • the aqueous solution may also be preheated, optionally to about the desired reaction temperature, prior to combining with the hydrogen and feed oil.
  • the quantity of basic additive is preferably sufficient to allow for at least about 90%, optionally at least about 95 or 99%, optionally substantially 100%, removal of targeted contaminants.
  • the basic additive may be in a molar excess over the acid contaminant or the conjugate base contaminant. If the contaminant is in the form of a conjugate base, the basic additive may be in at least about 0.9 mole equivalent relative to the conjugate base, or at least about 0.95, 0.99, 1, 1 .1, 1 .2 or 1.5 mole equivalent, or about 0.9 to about 2 mole equivalents, or about 0.9 to 1.5, 0.9 to 1.1 , 0.9 to 1 , 1 to 1 .5 or 1 to 1.2 mole equivalents, e.g. about 0.9, 0.95, 0.99, 1 , 1.1 , 1.2, 1 .3, 1 .4, 1.5, 1.6, 1 .7, 1 .8, 1 .9 or 2 mole equivalents.
  • the basic additive may be dissolved in water prior to combining the resulting basic solution with the feed oil. It will be recognized that the basic solution may be corrosive, and that the corrosiveness will depend in part on the concentration and type of the basic additive in the solution. As also noted elsewhere, sufficient water should be present to ensure that a dynamic liquid/vapour phase water equilibrium is present in the hydrogenation reactor. The ratio of water to feed oil required to achieve this will depend on the exact conditions used in the hydrogenation reactor. Thus it is preferred to use a sufficient ratio of water to basic additive so as to ensure that the basic additi ve and the contaminants remain mobilized by the water phase before and after catalytic reaction and that sufficient water is present during the reaction for the required equilibrium to be established.
  • the ratio of oil to basic solution will be between about 200: 1 and about 5: 1 on a volume basis using a basic additive concentration between 0.1 and about 10 molar.
  • the basic aditive concentration may be for example between about 0.1 and about 5, 0.1 and 2, 0.1 and 1 , 0.1 and 0.5, 0.5 and 10, 1 and 10, 2 and 10, 5 and 10, 1 and 5 or 0.5 and 2M, e.g. about 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 , 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9 or l OM.
  • the basic additive may have a pKb at standard temperature and pressure of between about 0.1 and about 5, or about 0.1 to 4, 0.1 to 3, 0.1 to 2, 1 to 5, 2, to 5, 3 to 5, 1 to 4, 2 to 5 or 3 to 4.5, e.g. about 0.1, 0.2, 0.3, 0.4, 0.5, 1 , 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5.
  • the outlet oil from the reactor will contain the oil and may additionally comprise one or more of reduction products from the contaminants, salts (e.g. obtained from the contaminants or from reduction products thereof), water, unreacted hydrogen and gaseous by-products of hydrogenation,
  • This mixture is at elevated temperature and pressure as it exits the hydrogenation reactor and may be passed to a cross exchanger where some of its heat energy is recovered so as to preheat reagents etc. (e.g. one or more of feed oil, hydrogen, aqueous solution) prior to their entering the reactor. It may then be passed to a high pressure gas-liquid separator. This is primarily to remove gaseous hydrogen and gaseous hydrogenation by-products from the oil stream.
  • the gas stream leaving the high pressure gas-liquid separator will primarily contain hydrogen gas and will often also contain some hydrogen sulfide and volatile oil components such as high volatility hydrocarbons. It may also contain some water vapour.
  • This gas stream may then be mixed with water or cold oil. This serves to cool the stream and condense and/or entrain the components of lower volatility. Alternati vely the stream may be cooled using a cooler or heat exchanger. The entrained lower volatility components may then be separated from the hydrogen stream in a hydrogen separator (gas-liquid separator). The gaseous stream, which is now largely hydrogen, may then be passed to a scrubber so as to further purify it and the scrubbed hydrogen may then be recycled into the reactor.
  • the scrubber may remove contaminants such as sulfides and mists. Suitable scrubbers, and methods for scrubbing, are well known in the art. It may for example be or comprise a water scrubber, an oxidant (e.g.
  • the liquid stream exiting the hydrogen separator contains water together with the recoverable oil components. These may then be separated from one another in a liquid-liquid separator and the non-aqueous (commonly predominantly
  • the oil stream having had most of its hydrogen removed in the high pressure gas-liquid separator, may be depressurized, commonly to approximately ambient pressure, and then passed to a liquid-liquid separator so as to remove waste water therefrom. It is at this point at which much of the water added at an early stage of the method may be removed from the oil, together with dissolved materials including hydrogenation byproducts, water soluble impurities which persist from the feed oil, salts etc.
  • the oil stream from the high pressure gas-liquid separator described above may be passed to a low pressure gas-liquid separator.
  • low pressure refers to pressures at or about or somewhat above atmospheric pressure (commonly about 100 to about 500kPa), but lower than the pressure of the high pressure gas-liquid separator.
  • the purpose of this separator is to remove any residual oil-soluble high volatility substances from the oil stream which might otherwise compromise product quality.
  • This separator commonly simply vents the oil stream at around ambient pressure so as to allow residual volatiles to flash off.
  • the high pressure gas-liquid separator is not used. In this alternative, the oil from the reactor is passed directly to the low pressure separator.
  • Vented gases would then include substantial amounts of unreacted hydrogen together with volatile oil components.
  • the hydrogen may then be separated from oil components, scrubbed and recycled to the reactor as described above, following recompression and, if necessary, further purification, and the volatile oil components returned to the oil stream also as described above.
  • the return may be before the low pressure gas-liquid separator, or may be into the low pressure gas-liquid separator.
  • the reduction in pressure of the oil may occur in a single step or may be conducted in a number of steps.
  • the pressure may be reduced in a pressure reduction valve following the high pressure gas-liquid separator.
  • it may reduce pressure somewhat in the high-pressure gas-liquid separator and then reduce pressure sufficient to pass to the low pressure gas-liquid separator in a separate pressure reduction valve.
  • Other alternatives will be readily apparent to the skilled person.
  • a useful option that may be used in conjunction with the present invention is the use of a degassing or stripping step.
  • the oil which comes from the reactor may be stripped in a degassing unit. This may serve to improve the quality of the product refined oil. It is thought that sulfur compounds which are frequently present in the feed oil may at least partially persist through the reduction step or may be converted at least in part to compounds which are difficult to remove, or are incompletely removed, in the high and low (i.e. approximately ambient) pressure gas-liquid separators.
  • Sulfur compounds which may exit the high pressure reactor in the oil include hydrogen sulfide and other trace sulfides and bisulfides such as ammonium hydrosulfide. This may in part be due to the relatively low volatility of some of these compounds and/or to the elevated raiscibility of some of the compounds at elevated pressure and may also in part be due to the relatively high solubility in the oil of related sulfide compounds. The continued presence of such compounds compromises product quality.
  • a stripping (degassing) step may be introduced into the process. This commonly applies moderately elevated temperatures and reduced pressure to the oil stream so as to remove sparingly volatile or entrained substances although other stripping methods are also
  • the pressure is commonly less than about 90kPa, or less than about 80, 70, 60, 50, 40, 30, 20, 10, 5, 4, 3, 2 or lkPa, or about 0.1 to about 90kPa, or about 0.1 to 50, 0.1 to 10, 0.1 to 5, 0.1 to 1 , 0.1 to 0.5, 1 to 10, 2 to 10, 5 to 10, 1 to 5, 1 to 90,
  • 10 to 90, 50 to 90, 10 to 50 or 2 to 5kPa e.g. about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 , 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80 or 90kPa.
  • These pressures are absolute pressures.
  • a pressure of l OkPa for example, will be equivalent to a pressure of around -90kPaG (i.e. 90kPa below atmospheric pressure).
  • a higher temperature will generally allow for a less strong vacuum (i.e. higher pressure).
  • the conditions used for this stripping step may be sufficient to remove sufficient volatile materials that the resulting refined
  • the time for stripping is commonly about 0.5 to about 10 minutes, or about 0.5 to 5, 0.5 to 2, 0.5 to 1, 1 to 10, 2 to 10, 5 to 10, 1 to 5 or 2 to 5 minutes, e.g. about 0.5, 1 , 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9 or 10 minutes, but may be longer or shorter than this.
  • This aspect of the process has been described in provisional application AU2014900905 and in International Application PCT/AU2014/000687 which claims priority therefrom, the entire contents of both of which are incorporated herein by cross-reference.
  • the stripping/degassing step described above be conducted before the oil is exposed to any relatively more oxidizing conditions than pertain immediately after the product mixture leaves the hydrogenation reactor, or before exposure to any oxidants.
  • This step may be conducted under reducing conditions. It may be under non-oxidising conditions.
  • the oil exiting the reactor may be maintained under non-oxidising conditions until after it exits the degassing unit. Oil exiting the reactor retains a certain amount of hydrogen. It may be hydrogen rich and may be hydrogen saturated. It is therefore under relatively reducing conditions. If the oil is subjected to relatively more oxidising conditions before the stripping/degassing step, some reactor product components may react (e.g.
  • oxidise and thereby may persist in the oil or be rendered more difficult to remove in the stripping/degassing step. This may result in these compounds or compounds derived therefrom persisting in the final product oil. These may cause the oil to fail certain of the standard quality tests described earlier. It is therefore desirable to prevent such reactions. This may be achieved by maintaining chemically non-oxidising conditions in the oil until after the stripping step. It may be facilitated by use of piping and other components between the reactor and the degasser which prevent ingress to the oil of oxidants such as oxygen.
  • the degassing unit used for the degassing step described above may be for example a vacuum tank degasser. This may comprise a horizontal, vertical or round vessel. A vacuum is created in the vessel. As well as serving to remove volatiles, this can also draw the oil into the tank. When the oil enters the tank, it may be atomised or sprayed into the vessel or may be distributed to a layer of internal baffle plates or other high surface area device designed for the oil to flow in a thin, commonly laminar, film, and is exposed to a vacuum that forces volatile materials to escape from the oil.
  • the degassing or stripping may comprise atomising or spraying the oil into a vacuum chamber by means of one or more nozzles.
  • the vacuum pump passes the escaping volatiles from the vessel and discharges them, preferably after scrubbing to remove toxic products.
  • a cyclonic stripping unit may be used, in which the oil passes in a thin film around the inner walls of a vessel whilst a vacuum is applied to the inside of the vessel.
  • the stripped oil exiting the degassing unit may have undesirable volatile components stripped from it. It shoul d be understood that there may be a residual level of volatiles, however these will generally be of a form, concentration and chemistry that is compatible with product quality objectives. They may be present at a level which is acceptable for subsequent use, for example as a transformer oil, and may be present at a level sufficiently low to meet relevant industry and/or regulatory standards. Following the stripping/degassing, it may be beneficial to extract the oil stream with water. This comprises the steps of adding water to the oil stream exiting from the degassing unit and subsequently separating the water from the oil stream so as to remove water soluble components such as salts.
  • It may comprise the step of agitating the oil and water stream so as to improve contact and hence improve extraction. It may also comprise the step of drying the oil stream after separating the water therefrom, so as to remove any residual water that may be present.
  • the water extraction may be conducted using any suitable water extraction device, for example an in-line mixer, a countercurrent extractor etc.
  • the present invention in one form represents a method for reducing or preventing catalyst fouling and/or poisoning during catalytic hydrogenation refining of oil, particularly hydrocarbon oils.
  • Contaminants in these oils may include metal-complexing agents. They may for example include any one or more of phosphorus, phosphate, alkylated phosphate and thiophosphate, carbamate, sulfurs, sulphonated and sulphated additives and detergents, other de- metallised alkylated ligands, glycols, esters and oxidised mineral hydrocarbon oil.
  • the method may produce refined and/or purified hydrocarbon, which may be suitable either for fractionation to produce high quality fuel and base oils, or for further processing to produce higher quality base oil or fuel.
  • a controlled pH separable water phase is introduced into the dynamic reaction system.
  • a controlled water feed is provided along with feed oil to a hydrogenation reactor to control reaction conditions, reactant and product partitioning and reactant equilibria in a dynamic multiphasic reaction environment.
  • This may be achieved by combining the feed oil with pH adjusted water where the pH is adjusted using a stronger conjugate base than the corresponding conjugate base in the feed impurity at a rate such that resultant salt can be fully solubilised by the pH adjusted water phase. It is hypothesized that this prevents the acid or conjugate base thereof from poisoning the catalyst, since the basic additive in the pH adjusted water can displace any conjugate base interacting with the catalyst surface. Consequently the acid or conjugate base remains in the water phase and can be removed from the hydrogenation reactor.
  • Suitable ratios may result in the presence within the reactor of a free phase of water. They may ensure that there is sufficient water phase to maintain adequate mobility and solubility of salts.
  • the method of the present invention may be practiced as a continuous process, although in some cases it may be alternatively practiced as a batchwise process.
  • ratios of reactants etc, described herein should be taken to be ratios of fl ows of those reactants.
  • the pH adjusted water may be added to the oil at an oikwater ratio of between about 200: 1 and 5: 1 on a volume basis, when practiced as a continuous process this requires the flow rate of the oil to be between about 5 and 200 times that of the water on a volume basis.
  • the hydrogen may be introduced into the oil at a pressure of about 2 to about 18MPa, or about 2 to 15, 2 to 10, 2 to 5, 5 to 15, 10 to 15, 3 to 10 or 5 to l OMPa, e.g. about 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17 or 18M Pa. It may be introduced into the oil at a pressure below the critical pressure of water. These pressures may pertain in the hydrogenation reactor (i.e. they may refer to the reaction pressure).
  • the hydrogen may be introduced in a sealed system so as to produce suitable reducing conditions.
  • the reaction mixture comprising the feed oil, hydrogen, a basic additive and water, may be heated to a reaction temperature of between about 200°C and about 500°C.
  • the temperature will commonly be below the critical temperature of water (about 374°C).
  • the reaction temperature may be between about 200 and 400, 200 and 300, 300 and 500, 300 and 400, 250 and 350, 250 and 374 or 300 and 374°C, e.g. about 200, 250, 300, 310, 320, 330, 340, 350, 360, 370, 374, 380, 390, 400, 450 or 500°C.
  • the pressure in the reactor should be such that at least some of said aqueous solution exists as a partially condensed vapour.
  • the vapour-liquid phase boundary of the phase diagram It is preferably a pressure at or about the vapour-liquid phase boundary of the phase diagram at the selected reactor temperature. It may be within about 10% of the pressure at or about the vapour-liquid phase boundary at the selected reactor temperature, or within about 9, 8, 7, 6, 5, 4, 3, 2 or 1 % thereof. It may be a pressure on the liquid side of the vapour-liquid phase boundary of the phase diagram.
  • the temperature and pressure in the hydrogenation reactor may be sub- critical, i.e. the temperature and pressure should not both be above the critical point for water.
  • the heating may be by means of a simple heat exchanger or heater, which may be electrical or may be a combustion heater or some other suitable heater.
  • the reaction mixture or at least a portion thereof e.g.
  • the feed oil/hydrogen mixture prior to combination with water and basic additive may be preheated before this heating by passing through a cross-exchanger in which heat is transferred from the product mixture exiting the hydrogenation reactor to the reaction mixture or portion thereof. It is preferred that within the hydrogenation reactor, the conditions are maintained below the critical point for water and around or below the phase transition of water between liquid and vapour (i.e. biased towards the liquid phase, or within the liquid region of the water phase diagram) so as to ensure the presence of discrete vapour and liquid water phases.
  • the heated reaction mixture is exposed to a hydrogenation catalyst in a hydrogenation reactor.
  • the hydrogenation catalyst is commonly a heterogeneous catalyst, i.e. it is not soluble in the reaction mixture.
  • the reaction may be passed over and/or through a fixed bed of hydrogenation catalyst at the reaction temperature and pressure as described above.
  • the catalyst may be present in the hydrogenation reactor in the form of a supported catalyst, a packed bed or a fluidized bed or in some other form.
  • reaction mixture After the reaction mixture passes out of the hydrogenation reactor, it may be cooled. It may be at least partially depressurized. The resulting product stream may then be separated into oil, water (now wastewater) and gas phases. The oil phase may be collected as the primary product.
  • the gas phase which consists mainly of hydrogen may be recycled into the process, commonly after scrubbing to remove acidic gases such as hydrogen sulfide.
  • the gas phase may also remove some hydrocarbon products which may be condensed and returned to the oil phase.
  • it is advantageous to maintain the gas phase at high pressure so as to reduce the energy required to recompress it to a suitable pressure for reaction in the
  • Filtered feed oil 10 is blended with an aqueous solution 5 that has a pH adjusted by the addition of a basic additive 30 and then pumped into a recirculating hydrogen stream 20.
  • Nra ' refers to m ⁇ as measured at standard temperature and pressure (25°C/1
  • aqueous solution 5 after combination with basic additive 30, may be added to the feed oil/hydrogen stream after heat exchanger 70 and before reactor 80.
  • the combined reactor product from separators 90 and 130 is depressurised, further cooled in exchanger 140 and passed to a final liquid/liquid separator 240 where water and salts are separated from the final product and the oil is recovered as a hydrogenated oil product suitable for fractionation or further processing.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé permettant de réduire la concentration d'un contaminant dans une huile. Dans le procédé un mélange de l'huile, d'un atome d'hydrogène et d'une solution aqueuse d'un additif de base est exposé à un catalyseur d'hydrogénation à une température de réaction comprise entre 250°C et 500°C et à une pression de réaction suffisante pour qu'au moins une partie de ladite solution aqueuse existe sous la forme d'une vapeur partiellement condensée à ladite température de réaction pour former un mélange de produits. L'huile est ensuite séparée du mélange de produits.
PCT/AU2015/000331 2014-06-05 2015-06-03 Purification d'huiles WO2015184487A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1409995.6 2014-06-05
GB1409995.6A GB2526855A (en) 2014-06-05 2014-06-05 Purification of oils

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