CN102159677B - Method for breaking emulsions containing hydrocarbons and compositions prepared by same - Google Patents
Method for breaking emulsions containing hydrocarbons and compositions prepared by same Download PDFInfo
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- CN102159677B CN102159677B CN200980136181.8A CN200980136181A CN102159677B CN 102159677 B CN102159677 B CN 102159677B CN 200980136181 A CN200980136181 A CN 200980136181A CN 102159677 B CN102159677 B CN 102159677B
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- 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
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
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Abstract
This invention relates to compounds and methods for preparing and breaking emulsions of water and hydrocarbons with asphaltenes. The solutes of this invention include chaotropes and kosmotropes, which decrease or increase the order of water molecules respectively. Aggregated asphaltenes form a coalescing barrier at the oil-water interface to result in a stable emulsion and keep water droplets from uniting. Conversely, dispersed asphaltenes allow a coalescing interface at the oil-water interface to resolve the emulsion and allow water droplets to unite. Some applications of this invention include crude oil processing, refinery applications and water treatment methods.
Description
Technical field
The present invention relates to the compound of the hydrocarbon emulsion of preparation and destruction asphaltenes.
Background technology
The trend of refining at present comprises utilizes heavy crude and alternative hydrocarbon source, as pitch and tar sand.The bitum amount that these heavy material comprise increases, and has caused the difficulty of processing causing because of viscosity, fouling and emulsion problem etc.
Owing to always may not controlling oil property or being useful on refinery steams to prevent the composition of fouling, therefore other can be controlled and/or be managed bituminous matter, especially have demand and expectation about material or the technique of emulsion.In some cases, it is favourable forming emulsion, and in other cases, breakdown of emulsion is favourable.
As the response to this demand, oil-refinery industry has launched effort and has developed novel method to solve the problem relevant to asphaltenes logistics emulsion with resource.But in the practical approach and the composition aspect that provide for controlling emulsion, these effort only obtain part success.
The people's such as Durrieu United States Patent (USP) 5,154,857 disclose water-soluble breakdown of emulsion and the scale inhibitor of tetraalkyl ammonium salt halogenide and at least one poly-alkoxylation Alkylenediamine for crude oil desalting and dehydration (polyalkyloxylated alkylenediamine) or its vitriol.The open Compounds and methods for that had not only formed but also destroyed emulsion of the people such as Durrieu.
The people's such as Watkins United States Patent (USP) 4,775,489 disclose for stimulate the hole stopped up because of wax deposition from breakdown of emulsion formula spumescence emulsion oil-in-water.Said composition needs: 1) organic solvent, 2) liquid, aqueous, 3) rare gas element, and 4) tensio-active agent.
The people's such as Huang United States Patent (USP) 6,262,168 discloses the water dispersion of the water-soluble cationic polymer of interpolation lyophily agent (kosmotropes) and chaotropic agent, is used for water treatment industry as viscosity-depression agent.
In field of biology, the people's such as Knowles United States Patent (USP) 4,658,022 discloses chaotropic agent and has made the application of (folding) protein denaturation.But, Knowles fail teaching or suggestion chaotropic agent is used together with hydrocarbon or bituminous matter.
Although aforementioned disclosure provides technical progress,, still there is demand for the method for destroying and form the emulsion that contains bitum hydrocarbon stream.
Summary of the invention
These and other aspect of the present invention relates at least partly uses lyophily agent (kosmotropes) and/or chaotropic agent control bituminous matter to form and/or to destroy method and the compound of emulsion.
According to an embodiment, the present invention relates to comprise the composition of matter that exceedes a liquid phase, wherein said composition comprise comprise bitum hydrocarbon phase and comprise lyophily (kosmotropic) solute and/or from liquid solute containing water.
According to another embodiment, the invention still further relates to the method for destroying or form emulsion in the application of hydrocarbon, the method comprises to be made to comprise bitum hydrocarbon phase and comprises lyophily solute and/or merge mutually from the moisture of liquid solute.
According to another embodiment, the present invention relates to, by hydrocarbon stream and water logistics are merged, in the application of hydrocarbon, destroy the method for water-in-oil emulsion.Described hydrocarbon stream comprises water-in-oil emulsion and bituminous matter, the solute of the character that described water logistics comprises at least one change at least a portion water.Described merging forms continuous water and oil-continuous phase.The method further comprises makes continuous water separate with oil-continuous phase.
According to another embodiment, the present invention relates to remove and/or be reduced by least a part of bitum method from hydrocarbon stream, the method comprises merges hydrocarbon stream and water logistics.Described hydrocarbon stream comprises bituminous matter, and described water logistics comprises at least one and make the solute of a part of water modification.Described merging forms at least one emulsion, at least one waterbearing stratum and at least one hydrocarbon layer.Ideally, described emulsion comprises water-in-oil emulsion or emulsion oil-in-water.The method further comprises makes waterbearing stratum and hydrocarbon layer and separation of emulsions.
According to another embodiment, the present invention relates to by making to comprise bitum hydrocarbon phase and comprising lyophily solute and/or merge mutually the method for the analytical test of the emulsion that quickening contains hydrocarbon and aqueous solution from the moisture of liquid solute.The method further comprises and forms or decompose emulsion, to produce a layer or multiple layer, and measures one or more features of this layer or multiple layers.
According to another embodiment, the present invention relates to form the method for emulsion, it comprises makes hydrocarbon and hydration also, and bituminous matter is assembled, to form coalescent barrier.Or, the present invention relates to breaking method, described method comprises makes bituminous matter disaggregation, to remove at least in part coalescent barrier, and makes water droplets coalescence.
Brief description of the drawings
From following detailed description above and further feature and the aspect that the present invention may be better understood based on accompanying drawing, wherein:
Fig. 1 has shown according to an embodiment, the form of solute concentration to the water decompositing from emulsion;
Fig. 2 shown according to an embodiment, the first sample of stable emulsion and resolved into the second two-layer sample by solute;
Fig. 3 A has shown the bituminous matter in the absorption of water droplet interface;
Fig. 3 B shown according to an embodiment, after processing with solute in the bituminous matter of the minimizing of water droplet interface;
Fig. 4 has shown according to an embodiment, the form of solute concentration to the water decompositing from emulsion;
The bituminous matter of gathering when Fig. 5 A has shown without solute;
Fig. 5 B has shown according to an embodiment, the bituminous matter of the gathering while having some solutes;
Fig. 5 C shown according to an embodiment, the bituminous matter of the gathering while having than the many solute of Fig. 5 B;
Fig. 6 has shown according to an embodiment, containing the graduated centrifuge tube of separative emulsion; With
Fig. 7 has shown according to the schema of the dehydrating of crude oil of an embodiment.
Detailed Description Of The Invention
Term used herein " bituminous matter " general reference sees crude oil, pitch, tar sand, coal, the molecular substance of middle refinery steams and/or analogous material.Bituminous matter refers generally to further comprise hydrogen, sulphur, nitrogen, and/or the poly-aromatic carbon material of metal.What conventionally, bituminous matter was defined as carbonaceous material in operation is insoluble to normal heptane (C
7h
16) but be dissolved in toluene (C
6h
5cH
3) component.Bituminous matter can comprise at least one polarity section and/or part.Each bituminous matter frequent Cheng Geng great and/or more complicated structure.Bituminous matter can show as the suspended solids in hydrocarbon, but can distinguish as mineral deposit with other suspended matter.
Bituminous matter aggregate can be stablized water-in-oil emulsion in the time of water-oil interface set.Bituminous matter aggregate can form barrier and stop coalescent between water droplet.According to an embodiment, form bituminous matter aggregate at water-oil interface place by stoping, water can be more easily coalescent, and improve water and oil separating.
The material that mainly and/or substantially comprises carbon and/or hydrogen atom made a general reference in term used herein " hydrocarbon ".Hydrocarbon further can comprise other atom, as nitrogen, and oxygen, sulphur, metal and/or similar atom.Hydrocarbon material source includes but not limited to fossil oil, crude oil, and tar sand, pitch, coal, peat, biomass, building-up reactions thing, and/or any other suitable material is supplied with.According to an embodiment, hydrocarbon of the present invention has been got rid of by amino acids formed molecule, as protein.
Term used herein " BS & W " general reference is by ASTM D1796, ASTM D9570, API 2548, API 2560 and definite basic sediment and the water of any other suitable test, BS&W, and/or bottom solid and water.More than be mentioned the text of test to be incorporated herein by reference.BS & W generally include from hydrocarbon material as former oil supply tank bottom extract and/or separate solid, water and emulsion.
Term used herein " merging " refers to two kinds or above article, material and/or logistics mixing, closely mixes, and contact, and/or put together.
Term used herein " moisture " general reference mainly and/or substantially comprises water (H
2o) material.Hydrous material and/or solution further can comprise one or more other materials, as in solution and/or suspension.Water comprises at least slightly polarity, so that can affect the absorption of bituminous matter to water-oil interface.For example, water also comprises hydrogen bond and/or other weak molecular force.
The mixture of two kinds of unmixing materials of term used herein " emulsion " and " dispersion " general reference, wherein a kind of species distribution and/or be blended in the second material.Exemplary emulsion comprises former water-in-oil-type, hydrocarbon water-in type, water bag hydrocarbon type and/or similar emulsion.Emulsion also comprises water-in-oil-type, and oil-in-water-type and/or its combination, as water-in-oil oil-in or water-in-oil-in-water type.The latter can be called as complexity and/or composite emulsion sometimes.
Term used herein " stable emulsion " is made a general reference under for example about 1G power and environment (indoor) temperature condition, being less than the emulsion that does not significantly resolve into two or more layers in approximately 30 days.
Term used herein " unstable emulsion " is made a general reference under for example about 1G power and environment (indoor) temperature condition, significantly resolves into the emulsion of two or more layers in about 24h.
The physics distinctiveness form of term used herein " phase " general reference material.Can be continuous, discontinuous and/or discrete mutually.
The discrete expansion of term used herein " layer " general reference material, be generally horizontal development and/or layer.
The barrier of bituminous matter, inoganic solids, metal and/or the metal complex of term used herein " coalescent barrier " general reference bituminous matter, gathering, wall, hamper, and/or obstacle.Coalescent barrier conventionally but not necessarily forms and/or around water droplet around water droplet, to prevent, to block and/or to reduce and the coalescent of other water droplet and/or merge.In fact, as a part for sepn process, bituminous matter hinders and/or has suppressed water droplet and got together.A part for coalescent barrier can optionally comprise inoganic solids.
Mutually and/or the intersection of layer, water droplet can merge and not pass through bituminous matter barrier and/or other similar hamper there for term used herein " coalescent interface " general reference.
The mixture of miscible material made a general reference in term used herein " solution ", and wherein a kind of substance dissolves is in the second material.
The material of the dissolving solute in term used herein " solvent " general reference solution.The amount of the solvent existing in solution conventionally but be not necessarily greater than other material.
In term used herein " solute " general reference solution by the material of dissolution with solvents.Solute can comprise solid, liquid, and/or gas.Ideally, solute of the present invention comprises relatively simple molecule, and can get rid of for example polymer materials.Solute can be made up of single compound ideally, and/or alternatively, comprises for example multiple compounds.
Term used herein " lyophily " or " lyophily agent " general reference, under the condition of bound by theory not, is believed to be helpful in the material of the interactional stability of water-water and structure.Lyophily agent makes water molecules advantageously interact conventionally, and this has also stablized macromole as bitum molecular interaction.Lyophily agent can be ion and/or non-ionic.Ideally, the lyophily agent sub order that moisturizes.
Lyophily agent conventionally but not necessarily tend to be little and/or have high charge density.The agent of exemplary ion lyophily comprises vitriol, phosphoric acid salt, magnesium (2+), lithium (1+), and/or any other suitable material.For example,, according to the hydration free energy of salt (Δ G
hydr), negative Δ G
hydrincrease gradually cause this salt to have more lyophily.Other suitable lyophily agent can comprise vitriol, phosphoric acid salt, hydrophosphate, ammonium sulfate, sodium sulfate, Citrate trianion, oxalate, and/or the material of any other increase order.Gegenion can comprise IA family metal ion, IIA family metal ion, ammonium ion, and/or other suitable ion.
The agent of nonionic lyophily conventionally but not necessarily there is no net charge, but is easy to dissolve, and becomes easy hydration.
Term used herein " from liquid " or " chaotropic agent " general reference, under the condition of bound by theory not, are considered to the material of the three-dimensional structure of destroying water.Chaotropic agent disturbs the stablizing as the intramolecular interaction of hydrogen bond, Van der Waals force and/or hydrophobic interaction mediation by noncovalent force conventionally.Exemplary chaotropic agent comprises urea, Guanidinium hydrochloride, lithium perchlorate and/or any other suitable material.Ideally, chaotropic agent reduces the order of water molecules.In some embodiments, water soluble chloride is excluded outside possible chaotropic agent.
Some inorganic, organic and/or mixing salts can be by for example shielding electric charge and stoping the stable of salt bridge to possess from fluidity matter.Conventionally, hydrogen bond is stronger in nonpolar medium, and therefore, the salt that increases the moment of dipole of solvent also can make hydrogen bond unstable.Or the ion that heavy ion or electric density are low serves as chaotropic agent, as bromide, iodide, potassium (1+), caesium (1+), and/or any other suitable material.Other suitable chaotropic agent can comprise thiocyanate-, perchlorate, oxymuriate, nitrate, bromide, iodide, anion surfactant and negatively charged ion hydrotropisms salt, alkyl and substituted alkyl sulfonate, dialkyl sulfosuccinates, diaryl sulfosuccinate, benzene sulfonate, benzene disulfonate, naphthalenesulfonate, the material of napadisilate and/or any other destruction order.
Term used herein " Gunhild Hoffmeister salt (Hofmeister salts) " or " hofmeister series (Hofmeister series) " general reference are according to the classification of ion in sequence of the ability of the change water structure of ion.In order to regulate water, can select negatively charged ion and cationic pairing, wherein every kind of ion changes the character of water to some extent.Negatively charged ion conventionally but not necessarily have greater role than positively charged ion.List exemplary ion by relative order and/or grade below.
Negatively charged ion: SO
4> HPO
4> acetate moiety > Cl > NO
3
Positively charged ion: Mg > Li > Na > K > NH
4
Under the condition of bound by theory not, we think, the mechanism of Gunhild Hoffmeister salt comprises the change of water structure and/or character, as the interactional change between ion, bituminous matter and/or water molecules.Some salt of this order have increased the surface tension of solvent while being dissolved in water, and change the solubleness of bituminous matter at water-oil interface place, thereby cause bituminous matter to precipitate from the oil of oil/water interface and/or " saltouing " out, for example, by strengthening aqueous favoring mutual effect.Ideally, solute of the present invention and/or salt regulate the character of water, to cause bituminous matter preferentially to interact with other hydrocarbon or water molecules (assemble or disperse).
Ideally, other salt in hofmeister series increases the solubleness of non-polar molecule while being dissolved in water, thereby causes bituminous matter dissolving and/or " salt is molten " in oil; For example,, by weakening hydrophilic interaction.These salt also can be directly and bituminous matter interact.The exemplary ion with strong " salt is molten " effect can comprise I
-and SCN
-, and can affect bitum set or gathering, secondary structure and/or tertiary structure.
The present invention has many kind application, and it includes but not limited to hydrocarbon processing, and crude oil extracts, field facility, pitch is removed, tar sand exploitation, coal measures system, concise operation, dewatering unit, desalting plant, crude unit, coker, hydrocracking device, deasphalting unit, oil fuel emulsion, hydrocarbon transport, oil spilling cleaning, wastewater treatment and/or any other suitable application.
According to an embodiment, can in the bath water of desalting plant, add lyophily and/or from liquid solute, wherein it is desirable to, solute more promptly makes oil hydrosol decompose, so that anti-sealing is taken to hydrocarbon layer and/or improves the dehydration of crude oil.Or solute of the present invention also can more promptly decompose emulsion, to prevent that oily movement from being brought to water layer downwards and/or reducing from the fuel load in the water logistics of desalting plant.
According to another embodiment, solute of the present invention makes the crude oil of at least a portion bituminous matter between interface and/or interruption (rag) layer, for example hydrocarbon layer and water layer concentrated.Ideally, phantom forms oil, water, solute and bitum emulsion, so that can from demineralizer, take out in mode continuous and/or that be interrupted.
According to an embodiment, lyophily of the present invention and/or also can add coking from liquid solute.Conventionally, some water add as vacuum residuum together with the raw material of coker.Before entering coking furnace, in the water that makes to add, containing solute can reduce stove dirt by for example making bituminous matter be retained in emulsion.Or the present invention can implement by adding solute to implement in any other suitable asphaltenes logistics.
For example, according to an embodiment, the solute of dry salt form mixes to decompose emulsion with water-in-oil emulsion or emulsion oil-in-water.Other suitable form of solute, comprises pill, powder, crystal, paste, slurry, enriched material etc., is all possible.
Orimulsion
be the registered trademark of Intevep, be used in the transport of heavy oil and/or pitch and combustion processes in the emulsion for reducing viscosity.Intevep is the research and development branch (Research and Development Affiliate of Petroleos de Venezuela SA) of South America Venezuelan Petroleum Company, also referred to as PDVSA.According to an embodiment, can be of the present invention from liquid solute to adding in water, stable when further making emulsion transport in for example pipeline and/or seagoing tanker.Then,, in the time reaching suitable point of destination, can add lyophily solute of the present invention to carry out for example breakdown of emulsion and reduce the water that is sent to for example fuel burner.Amount of heat and/or heat energy are usually used to make Orimulsion
in water evaporation and/or be heated to pitch fully and the temperature of active combustion.The water of removing before burning in emulsion can more effectively utilize fuel.
According to an embodiment, lyophily of the present invention and/or from liquid solute be used to increase as oil recovery rate in oil field, waste oil rectification systems and/or any other suitable application.Or solute can be for any in the process by transports such as such as pipeline, railcar, barge, ship, oil tanker, trucies, water and/or moisture and hydrocarbon coexist.A kind of useful application is to unship to carry the processing of removing the hydrocarbon in water ballast before.Ideally, solute also can be for helping cleaning hydrocarbon overspill and/or releaser.
According to an embodiment, lyophily of the present invention and/or can be with helping dehydrating of crude oil from liquid solute, as by drawing water from storage tank bottom in refining first being processed.
According to an embodiment, lyophily of the present invention and/or help laboratory method from liquid solute, as by than without more promptly decomposing emulsion in solute situation, the suitable like this result that makes is faster and accurately.Or solute makes emulsion-stabilizing, and make result faster and accurate.
According to an embodiment, use lyophily of the present invention and/or comprise the pH (neutrality, acidity and/or causticity) that regulates emulsion, dispersion, water and/or solution from the method for liquid solute.For example, solute can be acid, as in the time preventing that naphthenate from forming.Or, for example, alkali solute can with crude oil in metal reaction.
According to an embodiment, the present invention includes containing exceeding the composition of matter of a liquid phase, wherein said composition comprise the hydrocarbon phase of asphaltenes and containing lyophily solute and/or from liquid solute containing water.Solute can comprise Gunhild Hoffmeister salt mentioned above, non-ionic type molecule and/or ion salt.This exceedes a liquid phase can be for example continuous or discontinuous.
Ideally, solute changes the character containing at least a portion water in water, as changed hydrogen bond, strengthen polarity, reduce polarity, increase specific conductivity, reduce specific conductivity, increase surface tension, reduce surface tension, sub order moisturizes, reduce the order of water molecules, strengthen the stability of water-bituminous matter at oil-water interface, reduce the stability of water-bituminous matter at oil-water interface, and/or any other suitable character of water.Solute of the present invention can comprise any suitable compound.Ideally, solute does not comprise tensio-active agent and/or stain remover.Or solute can comprise tensio-active agent and/or stain remover.Ideally, solute can comprise with downstream refining processes compatible component, to cause for example corrosion and scaling and/or poisoning of catalyst to minimize.
In water, the amount of solute can any suitable amount exist.The sufficient quantity of solute can be in approximately 0.1 % by weight of the amount of formation saturated solution to forming between the amount of saturated or supersaturated solution, ideally, in approximately 1.0 % by weight of amount that form saturated solution to forming between approximately 90 % by weight of amount of saturated solution, more desirably, in approximately 1.0 % by weight of amount that form saturated solution to forming between approximately 70 % by weight of amount of saturated solution.
Composition of matter can comprise the bitum coalescent barrier of bituminous matter and/or gathering.Coalescent barrier conventionally but not necessarily forms and/or around water droplet around water droplet, to prevent and/or to reduce and the coalescent of other water droplet and/or merge.In fact, as a part for sepn process, bituminous matter hinders and/or has suppressed water droplet and got together.
Or composition of matter can comprise coalescent interface, as around water droplet conventionally not or have the bituminous matter of reduction and/or a bituminous matter of gathering, to allow and/or not reduce and the coalescent of other water droplet and/or merge.In fact, as a part for sepn process, bituminous matter is dispersed in hydrocarbon, not hinder and/or not suppress water droplet and get together.
According to an embodiment, present invention resides in the method for destroying or form emulsion in the application of hydrocarbon.Destruction and/or decomposition emulsion comprise makes at least considerable part separation of emulsions become two or more discrete external phase, is more preferably separated into two or more discrete layers.Form and/or prepare emulsion and comprise at least one phase producing from the water of water and/or oil sources and/or the mixture of oil, more preferably discrete layer.The method comprises to be made to contain bitum hydrocarbon phase and contains lyophily solute and/or merge mutually from the moisture of liquid solute.
The aqeous phase of hydrocarbon ideally but not necessarily form water-in-oil emulsion, emulsion oil-in-water, at least one hydrocarbon layer is together with at least one waterbearing stratum, and/or any other the suitable system producing.Water-in-oil emulsion can comprise a certain amount of water being dispersed in oily external phase and/or layer.Emulsion oil-in-water can comprise the oil in a certain amount of external phase and/or layer that is dispersed in water.
According to an embodiment, the method further comprises decomposes emulsion with lyophily solute, forms continuous hydrocarbon layer and continuous waterbearing stratum.Or the method further comprises using from liquid solute makes emulsion-stabilizing, forms one or more liquid phases, it comprises discontinuous oil phase, oil-continuous phase, discontinuous any other suitable system that contains water and/or produce containing water, continuously.
According to an embodiment, the method further comprises that at least a portion of its Crude Oil forms hydrocarbon phase by crude oil and bath water formation emulsion, and at least a portion of bath water forms containing water.The formation of emulsion ideally but not necessarily occur in desalting plant, as among for example mixing valve, static mixer and/or any other mixing equipment and/or afterwards.The method may further include uses electrostatic field to assist breakdown of emulsion, as by making water droplet coalescent from oil.The electrode of demineralizer can comprise one or more levels and/or the height for operating in container.Solute of the present invention can improve demineralizer operation, as passed through electrode by permission high voltage and reduced-current intensity.
According to an embodiment, the method further comprises formation and/or removes bitum coalescent barrier.Form and/or prepare coalescent barrier and can comprise the bitum amount that makes the bituminous matter of hydrocarbon water termination assemble and/or increase hydrocarbon water termination.Remove and/or reduce coalescent barrier and can comprise the bituminous matter disaggregation that makes hydrocarbon water termination and/or the bitum amount that reduces hydrocarbon water termination.
For example, coalescent barrier can be a part for stable emulsion system.Or for example, in the time removing coalescent barrier, water droplet merges decomposes emulsion, and can form phase and/or the layer of separation.
According to an embodiment, present invention resides in the method for destroying water-in-oil emulsion in the application of hydrocarbon, it comprises makes to contain water-in-oil emulsion and bitum hydrocarbon stream merges with the water logistics that contains at least one solute that changes the character of at least a portion water.Ideally, this merging has formed continuous water and oil-continuous phase.The method further comprises makes continuous water separate with oil-continuous phase.
Merge and can occur in groove, container, basin, separator and/or desalting plant with separating, and further comprise and for example use electrostatic field to assist breakdown of emulsion.Or, merge and comprise from hydrocarbon phase and remove metal with separating further, as nickel and/or vanadium.The metal being removed can be the form of porphyrin (porphyn) and/or other complex molecule.
Solute can comprise lyophily solute, from liquid solute and/or Gunhild Hoffmeister salt.According to an embodiment, solute comprises ammonium sulfate (breakdown of emulsion), Guanidinium hydrochloride (making emulsion-stabilizing), ammonium chloride (breakdown of emulsion), and/or Trisodium Citrate (breakdown of emulsion).Other suitable salt is all possible.Ideally, solute and water form coalescent interface at the edge of water and hydrocarbon, so that bituminous matter is dispersed in hydrocarbon away from coalescent interface.Or solute and water cause forming coalescent barrier at the edge of water and hydrocarbon, so that bituminous matter is assembled and concentrates as coalescent barrier from hydrocarbon.
According to an embodiment, the present invention includes and from hydrocarbon stream, remove the bitum method of at least a portion.The method can comprise that making to comprise bitum hydrocarbon stream merges with the water logistics of the solute that comprises at least one modification part water, makes to merge to have formed at least one emulsion, at least one waterbearing stratum and/or at least one hydrocarbon layer.Ideally, emulsion comprises water-in-oil emulsion and/or emulsion oil-in-water.The method further comprises makes waterbearing stratum and hydrocarbon layer and separation of emulsions.The method may further include hydrocarbon layer is separated with waterbearing stratum.The method can comprise makes two, three and/or more discrete layer separate as hydrocarbon layer, phantom and water layer.The method can occur in desalting plant.The method may further include in emulsion and adds at least one breakdown of emulsion salt, and wherein breakdown of emulsion salt comprises lyophily solute and/or from liquid solute.The interpolation of at least one breakdown of emulsion salt can occur in outside desalting plant, as in wastewater treatment equipment.
According to an embodiment, the present invention includes the method for the analytical test of accelerating emulsion, hydrocarbon and/or aqueous solution.The method comprises to be made to contain bitum hydrocarbon phase and contains lyophily solute and/or merge mutually from the moisture of liquid solute.The method further comprises formation or decomposes emulsion, to produce one or more layers, and measures this one or more features of one or more layers.Ideally, feature comprises volume fraction, massfraction, molar fraction, composition, density, proportion, optical property, boiling point, freezing point, and/or any other suitable attribute measured.
According to an embodiment, the present invention includes the method that forms emulsion, it comprises makes hydrocarbon and hydration also, and bituminous matter is assembled, to form coalescent barrier and/or to hinder coalescent interface.Ideally, this gathering comprises that adding at least one is selected from the solute of lyophily agent, chaotropic agent and combination thereof.
According to an embodiment, the present invention includes the method for breakdown of emulsion, it comprises makes bituminous matter disaggregation and/or dispersion, to remove at least in part coalescent barrier and/or to form coalescent interface; With make water droplets coalescence.Ideally, disaggregation comprises that adding at least one is selected from the solute of lyophily agent, chaotropic agent and combination thereof.
Embodiment
Embodiment 1
Relative heavy crude sample is mixed with water, produced even after several weeks also unseparated stable emulsion.Bituminous matter in this result and water and crude oil interacts, and forms stable emulsion consistent.The crude oil of same-type is mixed with the aqueous ammonium sulfate of 25 % by weight saturation ratios, 50 % by weight saturation ratios, 75 % by weight saturation ratios and 100 % by weight saturation ratios.As shown in Figure 1, in 15min, per-cent 0 % by weight of the water decompositing is increased to 55 % by weight.This result is astonishing and beyond thought, because adding of salt decomposed rapidly stable emulsion.The present embodiment demonstration, salt of the present invention can destroy and/or decompose stable emulsion.
Embodiment 2
As shown in Figure 2, prepare two parts of mixtures that wait water gaging and crude oil.First part of mixture produced water and oil at single opaque stable emulsion in mutually.Second part of mixture comprises ammonium sulfate, and this is a kind of Gunhild Hoffmeister salt.Second part of mixture produced the water layer of clarification above black oil reservoir, proves that ammonium sulfate has improved the separation of oil-water.
Embodiment 3
Extract the water-in-oil emulsion sample demineralizer from operating gear.Fig. 3 A has shown the bituminous matter that is adsorbed on water droplet interface, and it is stable indefinitely under typical demineralizer operational condition.Fig. 3 B has shown by lyophily solute of the present invention identical emulsion after treatment.This emulsion is destroyed, and bituminous matter on oil-water interface reduces.Solute is the ammonium sulfate of saturated solution.
Embodiment 4
The sample of different crude oils is mixed with water, all do not form obvious emulsion (water of 90 % by weight keeps separating in the layer separating).Add Guanidinium hydrochloride with the saturation ratio of 25 % by weight, saturation ratio, the saturation ratio of 75 % by weight and the saturation ratio of 100 % by weight of 50 % by weight.The per-cent of the water decompositing as shown in Figure 4, is reduced to 50 % by weight from 90 % by weight.The present embodiment demonstration, solute of the present invention can form emulsion in the situation that conventionally can not forming emulsion.
Astonishing and unexpectedly, as shown in Figure 4, identical solute of the present invention also comprises the dual capability that forms and destroy emulsion according to the difference of concentration.As do not have as shown in Fig. 5 A of Guanidinium hydrochloride, there is little bituminous matter at water droplet interface.Shown in Fig. 5 B of some Guanidinium hydrochlorides, Asphaltene adsorption is at water droplet interface.But Fig. 5 C that the amount of Guanidinium hydrochloride increases shows, the asphalt quality minimizing of water droplet interface.
Embodiment 5
The stable emulsion of crude oil and water is merged with the Trisodium Citrate that destroys this emulsion.The graduated tube that Fig. 6 shows is included in the water layer of bottom and the oil reservoir on top.
Embodiment 6
Some crude oil is not easy dehydration.As shown in Figure 7, crude oil is placed in to storage tank, and extracts water from this storage tank bottom.Then water and solute merge, and form saturated solution, and return to storage tank entrance.The solute adding helps dehydrating of crude oil by breakdown of emulsion.Remainder or excessive water from crude oil can be removed from system.
Embodiment 7
The laboratory desalination test of crude oil is limited to the crude oil that does not form popularity emulsion when those mix with water conventionally.The crude oil sample that forms stable emulsion is unsuccessfully to have formed stable emulsion when when the merging of laboratory bath water and crude oil in the analysis in laboratory.Astonishing and unexpectedly, in the bath water of laboratory, add lyophily salt of the present invention that oil is separated with water is thorough, and allow, under the condition that does not change oil composition, oil and the mixture of water are carried out to laboratory test.
Although described the present invention with regard to some preferred embodiment in above-mentioned specification sheets, and many details are set forth for illustrative purposes, but, it is evident that to those skilled in the art, the present invention has allowed other embodiment, and some details described in this specification sheets and claim can be carried out sizable change under the condition that does not deviate from fundamental principle of the present invention.
Claims (18)
1. comprise the composition of matter that exceedes a liquid phase, said composition comprises:
Comprise bitum hydrocarbon phase; With
The water that contains that comprises solute, wherein solute is selected from hydrophosphate, ammonium sulfate, Citrate trianion, oxalate and combination thereof,
Wherein the amount of solute in 0.1 % by weight of amount that forms saturated solution to forming between the amount of saturated or supersaturated solution.
2. the composition of claim 1, wherein solute is selected from ammonium sulfate, Trisodium Citrate and combination thereof.
3. the composition of claim 1 or 2, wherein solute does not comprise tensio-active agent or stain remover.
4. the composition of claim 1 or 2, wherein solute comprises ammonium sulfate.
5. the method for destroying emulsion, the method comprises:
Provide and comprise bitum hydrocarbon phase and contain water, and add solute, wherein solute is selected from hydrophosphate, ammonium sulfate, Citrate trianion, oxalate and combination thereof.
6. the method for claim 5, wherein aqeous water-in-oil emulsion, emulsion oil-in-water, at least one the hydrocarbon layer of being selected from mutually of hydrocarbon be together with at least one waterbearing stratum, and combination.
7. the method for claim 5 or 6, its further comprise with described solute make emulsion decompose, to form continuous hydrocarbon layer and continuous waterbearing stratum.
8. the method for claim 5 or 6, wherein the amount of solute in 0.1 % by weight of amount that forms saturated solution to forming between the amount of saturated or supersaturated solution.
9. the method for claim 5 or 6, it further comprises removes bitum coalescent barrier.
10. the method for the destruction emulsion of claim 6, the method comprises:
Hydrocarbon stream and water logistics are merged, described hydrocarbon stream comprises water-in-oil emulsion and bituminous matter, the solute of the character that described water logistics comprises at least one change at least a portion water, wherein said merging forms continuous water and oil-continuous phase, and wherein solute is selected from hydrophosphate, ammonium sulfate, Citrate trianion, oxalate and combination thereof;
Continuous water is separated with oil-continuous phase.
The method of 11. claims 10, wherein solute is selected from ammonium sulfate, Trisodium Citrate and combination thereof.
The method of 12. claims 10, wherein merges with separating further and comprises from hydrocarbon phase and remove metal.
The method of 13. claims 5, for remove at least a portion bituminous matter from hydrocarbon stream, the method comprises:
Hydrocarbon stream and water logistics are merged, described hydrocarbon stream comprises bituminous matter, described water logistics comprises at least one and makes the solute of a part of water modification, wherein merge and form at least one emulsion, at least one waterbearing stratum and at least one hydrocarbon layer, described emulsion comprises water-in-oil emulsion or emulsion oil-in-water;
In emulsion, add at least one breakdown of emulsion salt, wherein breakdown of emulsion salt is selected from hydrophosphate, ammonium sulfate, Citrate trianion, oxalate and combination thereof, makes waterbearing stratum and hydrocarbon layer and separation of emulsions; With
Make hydrocarbon layer and waterbearing stratum and separation of emulsions.
The method of 14. claims 13, wherein separates and occurs in demineralizer device.
The method of 15. claims 13 or 14, at least one breakdown of emulsion salt of wherein said interpolation occurs in outside demineralizer device.
The method of 16. claims 7, for accelerating the method for analytical test of emulsion, hydrocarbon and aqueous solution, the method comprises:
Make to comprise bitum hydrocarbon phase and the moisture merging mutually that comprises solute, wherein solute is selected from hydrophosphate, ammonium sulfate, Citrate trianion, oxalate and combination thereof;
Form or decompose emulsion, to produce one or more layers; With
Measure the one or more features in these one or more layers.
The breaking method of 17. claims 5, the method further comprises:
Make bituminous matter disaggregation, to remove at least in part coalescent barrier; With
Make water droplets coalescence.
The method of 18. claims 17, wherein disaggregation comprises interpolation ammonium sulfate or Trisodium Citrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/182,617 US20100025300A1 (en) | 2008-07-30 | 2008-07-30 | Controlling emulsion stability during fuel stock processing |
| US12/182,617 | 2008-07-30 | ||
| PCT/US2009/050504 WO2010014390A2 (en) | 2008-07-30 | 2009-07-14 | Controlling emulsion stability during fuel stock processing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102159677A CN102159677A (en) | 2011-08-17 |
| CN102159677B true CN102159677B (en) | 2014-07-09 |
Family
ID=41258681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980136181.8A Expired - Fee Related CN102159677B (en) | 2008-07-30 | 2009-07-14 | Method for breaking emulsions containing hydrocarbons and compositions prepared by same |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20100025300A1 (en) |
| EP (1) | EP2318483A2 (en) |
| CN (1) | CN102159677B (en) |
| AU (1) | AU2009276900B2 (en) |
| WO (1) | WO2010014390A2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120140213A1 (en) * | 2010-12-02 | 2012-06-07 | General Electric Company | Static desalter simulator |
| US20140259883A1 (en) * | 2013-03-15 | 2014-09-18 | Petrosonic Energy Inc. | Emulsion fuel from sonication-generated asphaltenes |
| US11186783B2 (en) * | 2016-01-04 | 2021-11-30 | Hpc Petroserv, Inc. | Optimization of a method for isolation of paraffinic hydrocarbons |
| US11339779B2 (en) * | 2017-09-27 | 2022-05-24 | Natural Gas Solutions North America, Llc | Containing fluid leaks on additive pumps |
| CN111500310B (en) * | 2020-04-15 | 2022-01-25 | 王达 | Crude oil composite demulsifier and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1360398A (en) * | 1970-10-02 | 1974-07-17 | Dow Corning Ltd | Method for treating emulsions of hydrocarbon oil and water |
| US4082867A (en) * | 1974-06-27 | 1978-04-04 | Amchem Products, Inc. | Oil emulsion removal and recovery of oil |
| US4299690A (en) * | 1978-02-21 | 1981-11-10 | Texaco Canada Inc. | Demulsifying petroleum emulsions with aryl sulfonates-oxyalkylated phenolformaldehyde resins and alkali metal halides |
| US5100582A (en) * | 1989-12-28 | 1992-03-31 | Nalco Chemical Company | Water soluble polymer as water-in-oil demulsifier |
| US5164116A (en) * | 1990-07-27 | 1992-11-17 | Huels Aktiengesellschaft | Demulsifiers for breaking petroleum emulsions |
| EP0985722A2 (en) * | 1998-09-07 | 2000-03-15 | Rohm And Haas Company | Method of inhibiting the formation of oil and water emulsions |
| US6566410B1 (en) * | 2000-06-21 | 2003-05-20 | North Carolina State University | Methods of demulsifying emulsions using carbon dioxide |
| WO2008020909A2 (en) * | 2006-08-16 | 2008-02-21 | Exxonmobil Upstream Research Company | Demulsification of water-in-oil emulsion |
Family Cites Families (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2312731A (en) * | 1938-10-19 | 1943-03-02 | Standard Oil Dev Co | Process and agent for breaking petroleum emulsions |
| US2319885A (en) * | 1940-10-08 | 1943-05-25 | Petrolite Corp | Process and composition for treatment of emulsions |
| US2342650A (en) * | 1941-09-08 | 1944-02-29 | Petrolite Corp | Process for breaking petroleum emulsions |
| US2427326A (en) * | 1945-02-13 | 1947-09-09 | Socony Vacuum Oil Co Inc | Treatment of mineral oil emulsions |
| US2442075A (en) * | 1945-07-13 | 1948-05-25 | Petrolite Corp | Process for breaking petroleum emulsions |
| US2828267A (en) * | 1955-08-03 | 1958-03-25 | Petrolite Corp | Process for breaking petroleum emulsions |
| US3928194A (en) * | 1972-10-26 | 1975-12-23 | Texaco Inc | Emulsion breaking method |
| AU533444B2 (en) * | 1978-09-28 | 1983-11-24 | Salusinszky, A.L. | Regeneration of used lubricating oils |
| US4204946A (en) * | 1979-02-12 | 1980-05-27 | Turbo Resources Ltd. | Process for removing metal contaminants from used lubricating oils |
| US4439345A (en) * | 1981-06-11 | 1984-03-27 | Marathon Oil Company | Demulsification of a crude oil middle phase emulsion |
| CA1207699A (en) * | 1982-01-25 | 1986-07-15 | Isao Honzyo | Process for the solvent deasphalting of asphaltene- containing hydrocarbons |
| US4431523A (en) * | 1983-06-24 | 1984-02-14 | Phillips Petroleum Company | Upgrading fuel fractions in a re-refined oil process |
| US4502948A (en) * | 1984-03-30 | 1985-03-05 | Phillips Petroleum Company | Reclaiming used lubricating oil |
| US4614236A (en) * | 1984-05-29 | 1986-09-30 | Union Oil Company Of California | Self-breaking foamed oil-in-water emulsion for stimulation of wells blocked by paraffinic deposits |
| US4775489A (en) * | 1984-05-29 | 1988-10-04 | Union Oil Company Of California | Self-breaking foamed oil in water emulsion for stimulation of wells blocked by paraffinic deposits |
| US4658022A (en) * | 1985-08-08 | 1987-04-14 | Molecular Diagnostics, Inc. | Binding of antibody reagents to denatured protein analytes |
| US4891131A (en) * | 1984-12-21 | 1990-01-02 | Tar Sands Energy Ltd. | Sonication method and reagent for treatment of carbonaceous materials |
| US4705622A (en) * | 1986-03-27 | 1987-11-10 | Exxon Research And Engineering Company | Process for dedusting shale-oil |
| FR2609648B1 (en) * | 1987-01-16 | 1990-12-14 | Total France | DESEMULSIFYING AND ANTI-FOULING AGENT CAPABLE OF SEPARATING WATER-HYDROCARBON MIXTURES, WHETHER EMULSIFIED, AND APPLICATIONS THEREOF |
| US5593573A (en) * | 1988-07-21 | 1997-01-14 | Chevron Research Company | Demetalation of hydrocarbonaceous feedstocks using sulfuric acid and salts thereof |
| US5036915A (en) * | 1988-11-10 | 1991-08-06 | Alberta Energy Company Ltd. | Method of reducing the reactivity of steam and condensate mixtures in enhanced oil recovery |
| US5460750A (en) * | 1993-08-10 | 1995-10-24 | Nalco Chemical Company | Phenolic resins and method for breaking crude oil emulsions |
| US5449463A (en) * | 1994-03-11 | 1995-09-12 | Nalco Chemical Company | Desalter wash water additive |
| US5795463A (en) * | 1996-08-05 | 1998-08-18 | Prokopowicz; Richard A. | Oil demetalizing process |
| US5733462A (en) * | 1996-10-03 | 1998-03-31 | Cytec Technology Corp. | Cationic water-soluble polymer precipitation in salt solutions |
| US5738794A (en) * | 1996-10-03 | 1998-04-14 | Cytec Technology Corp. | Cationic water-soluble polymer preciptation in salt solutions |
| US5921912A (en) * | 1997-12-31 | 1999-07-13 | Betzdearborn Inc. | Copolmer formulations for breaking oil-and-water emulsions |
| US6262168B1 (en) * | 1998-03-11 | 2001-07-17 | Cytec Technology Corp. | Aqueous dispersions |
| US6383368B1 (en) * | 1999-03-02 | 2002-05-07 | Champion Technologies, Inc. | Method for pretreatment of refinery feed for desalting the feedstock, and related additive |
| US7618822B2 (en) * | 2002-12-19 | 2009-11-17 | Bp Corporation North America Inc. | Predictive crude oil compatibility model |
-
2008
- 2008-07-30 US US12/182,617 patent/US20100025300A1/en not_active Abandoned
-
2009
- 2009-07-14 EP EP09790385A patent/EP2318483A2/en not_active Withdrawn
- 2009-07-14 CN CN200980136181.8A patent/CN102159677B/en not_active Expired - Fee Related
- 2009-07-14 AU AU2009276900A patent/AU2009276900B2/en not_active Expired - Fee Related
- 2009-07-14 WO PCT/US2009/050504 patent/WO2010014390A2/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1360398A (en) * | 1970-10-02 | 1974-07-17 | Dow Corning Ltd | Method for treating emulsions of hydrocarbon oil and water |
| US4082867A (en) * | 1974-06-27 | 1978-04-04 | Amchem Products, Inc. | Oil emulsion removal and recovery of oil |
| US4299690A (en) * | 1978-02-21 | 1981-11-10 | Texaco Canada Inc. | Demulsifying petroleum emulsions with aryl sulfonates-oxyalkylated phenolformaldehyde resins and alkali metal halides |
| US5100582A (en) * | 1989-12-28 | 1992-03-31 | Nalco Chemical Company | Water soluble polymer as water-in-oil demulsifier |
| US5164116A (en) * | 1990-07-27 | 1992-11-17 | Huels Aktiengesellschaft | Demulsifiers for breaking petroleum emulsions |
| EP0985722A2 (en) * | 1998-09-07 | 2000-03-15 | Rohm And Haas Company | Method of inhibiting the formation of oil and water emulsions |
| US6566410B1 (en) * | 2000-06-21 | 2003-05-20 | North Carolina State University | Methods of demulsifying emulsions using carbon dioxide |
| WO2008020909A2 (en) * | 2006-08-16 | 2008-02-21 | Exxonmobil Upstream Research Company | Demulsification of water-in-oil emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102159677A (en) | 2011-08-17 |
| AU2009276900A1 (en) | 2010-02-04 |
| AU2009276900B2 (en) | 2015-01-29 |
| WO2010014390A2 (en) | 2010-02-04 |
| EP2318483A2 (en) | 2011-05-11 |
| WO2010014390A3 (en) | 2010-04-01 |
| US20100025300A1 (en) | 2010-02-04 |
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