CN101434858A - Method for removing pollutant in oil - Google Patents
Method for removing pollutant in oil Download PDFInfo
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- CN101434858A CN101434858A CNA2008101752927A CN200810175292A CN101434858A CN 101434858 A CN101434858 A CN 101434858A CN A2008101752927 A CNA2008101752927 A CN A2008101752927A CN 200810175292 A CN200810175292 A CN 200810175292A CN 101434858 A CN101434858 A CN 101434858A
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Abstract
The invention discloses a method for removing pollutant in oil, which comprises procedures of: making oil raw material pass through permeable hydrophobic polymer film. Oil passing through the film has fewer pollutants relative to the oil raw material.
Description
Technical field
The present invention relates generally to remove the method for pollutent in deoiling and relate to the system that implements this method.
Background technology
Need to remove the pollutent in deoiling under many situations.A kind of situation is for example re-refining of useless engine oil of waste oil.
Many commercial runs produce a large amount of waste oil, and described commercial run comprises the commercial run in ocean, mining, steel mill, machinery, petroleum chemistry, electric power, automobile, building and the aircraft industry.
Between use and on-stream period, liquid pollutant such as water and solid pollutant may be present in the oil as the metal fragment owing to engine scuffing and damaged generation, consequently influence the works better of oil.
The burning of waste oil and discarded may polluting, generation has a strong impact on to environment.Because waste oil contains toxic chemical substance usually, so their existence in waterways and soil may polluted source and food source.This will influence the people's of these pollutents of contact health.Therefore, expectation is refining or reclaim waste oil, so that utilize again.
From economic consideration, waste oil can contain the base oil more than 90%.The efficient recovery of base oil is expected very much.
Can be by the refining waste oil of the whole bag of tricks.Traditionally, adopt acid treatment, for example add sulfuric acid, metal-salt is separated with the useful hydrocarbon component in the waste oil with particle, aromatic compound, organic acid, polar compound and dirt or dissolve.Yet this causes consuming a large amount of chemical, and produces very deleterious acid sludge, and this acid sludge must be disposed in refuse landfill, causes serious processing and environmental problem.
Waste oil can use thin-film evaporator, makes with extra care by evaporation/distillating method.Yet, the easy coking of this vaporizer, the mechanism and the processing unit of the filthy vaporizer of possibility.Coking causes by the hydrocarbon pyrolysis that pollutent in the waste oil causes, and takes place when the waste oil temperature rises to more than 300 ℃ in feedstream usually.But, the necessary routine cleaning of this vaporizer, this may cause a large amount of stop times.This method is not suitable for small-scale operation economically, and reason is demanding investment.
Waste oil can carry out hydrotreatment, improving color, colour stability, and the reactivity that reduces lubricating oil.In the hydrotreatment process, there are many reactions to take place, for example, the hydrogenation of desulfurization, denitrogenation and color bodies, alkene and aromatic hydrocarbons.Not desired components has been removed in these reactions, and forms the handling oil that quality improves.But too much duration of contact or temperature will cause coking, and the catalyzer of coking must carry out other treatment step before removing.In addition, may have such possibility: if leak or accidental release, gaseous by-product such as hydrogen sulfide and ammonia may be discharged in the environment.And the treatment unit that is used to handle waste oil may be corroded owing to the acidity of chemical by-product.
The another kind of method of refining waste oil is that it utilizes mineral membrane by the use membrane separation apparatus.
A kind of known two-step approach comprises that the use mineral membrane removes dust and use comprises that the adsorption step of solvent or chemical substance removes color and the smell that deoils.This method comprises, uses the mineral membrane of operating under high malleation and high temperature, and this high malleation is applied to charging one side of film.Mineral membrane for example pottery or stainless steel membrane is relatively expensive.And operating method (being high pressure and high temperature) is uneconomical, because it consumes big energy.Further, under hot conditions, film is easier to be oxidized.This oxidation will cause oily color blackening and oil quality to descend.
Another disadvantage is that most of mineral membranes are hydrophilic, so water pollutant can pass through film.The further dehydration of needs reduces the water-content in the penetrating oil.
Need provide a kind of remove deoil in the method for pollutent, it overcomes or to have alleviated above-mentioned one or more at least unfavorable.
If embodiment disclosed herein provides a kind of method of removing pollutent and need not consume chemical, will be an advantage.
Summary of the invention
According to first aspect, a kind of method of removing pollutent from oil is provided, comprise step: make oily raw material by permeable hydrophobic polymer film, formation has the still less penetrating oil of pollutent with respect to described oily raw material.
This method can further comprise step: make described penetrating oil by described or another permeable hydrophobic polymer film, removed from described oil up to all basically described pollutents.
This method can comprise step: the described oily raw material that is substantially free of non-Oil solvent is provided.The amount of the non-Oil solvent that exists in the described oily raw material can be less than being selected from following amount: by volume less than 20%; By volume less than 15%; By volume less than 10%; By volume less than 5%; By volume less than 1%.
According to second aspect, a kind of method of removing pollutent from oil is provided, may further comprise the steps:
Provide the oily raw material that contains pollutent in enclosed slot;
Provide a plurality of permeable hydrophobic hollow-fibre membranes in described enclosed slot;
Apply pressure to described permeable hydrophobic hollow-fibre membrane; With
Make to the described oily raw material of small part by described permeable hydrophobic hollow-fibre membrane, in the chamber of described permeable hydrophobic hollow-fibre membrane, form and have the still less penetrating oil of pollutent with respect to described oily raw material.
In one embodiment, the described step that applies comprises step: apply in negative pressure and the malleation at least a to described hollow-fibre membrane.In another embodiment, the described step that applies comprises step: apply the described chamber side of negative pressure to described hollow-fibre membrane, apply charging one side that just is being pressed onto described hollow-fibre membrane simultaneously.Advantageously, select this permeable hydrophobic polymer film, so that from oil, remove pollutent substantially, for example coloured contaminant and colourless pollutent.
In one embodiment, this method also comprises step: make described penetrating oil contact selected sorbent material, at least further partly to remove the coloured contaminant that wherein comprises.Sorbent material can be a Fuller's earth.More advantageously, and not through the described oil phase ratio of removing the method for coloured contaminant, disclosed method allows more coloured contaminant to remove from penetrating oil basically after the clay bleaching.Advantageously, select this permeable hydrophobic polymer film, getting rid of any water that in described oily raw material, exists basically, thereby water is removed from described penetrating oil substantially.Therefore, the hydrophobic polymer film stops water pollutant to enter described penetrating oil by described film.Advantageously, oily raw material or penetrating oil all needn't dewater.Advantageously, method as herein described is safe to environment, and reason is that described method does not need to use any solvent or the chemical substance that is used for oil dilution or purifying.Therefore, the processing of waste water or waste residue significantly reduces.
According to the third aspect, a kind of method of removing pollutent from oil is provided, comprise step: make oily raw material by a plurality of permeable hydrophobic hollow-fibre membranes, formation has the still less penetrating oil of pollutent with respect to described oily raw material.
According to fourth aspect, a kind of oily purification system is provided, it comprises:
Enclosed slot is used for holding therein oily raw material;
A plurality of permeable hydrophobic hollow-fibre membranes, it is installed in the described enclosed slot so that be immersed in substantially in the described oil; With
Vacuum source, it is communicated with the chamber side liquid of described hollow-fibre membrane, to be driven in the chamber that the described oily raw material of small part enters described film and to produce penetrating oil therein.
According to fourth aspect, a kind of motor oil is provided, it is by the waste oil manufacturing of purifying in according to the method for either side in first, second or the third aspect.
Definition
Following word used herein and term will have represented implication:
Term used herein " hydrophobic polymer " is interpreted as referring to that water wetting had resistivity or be not easy by any polymkeric substance of water-wet.Just to the polymer materials of olighydria affinity.Hydrophobic polymer has the water contact angle that approximately is equal to or greater than 90 degree usually.Exemplary hydrophobic polymer comprises, but be not limited to, polyolefine, for example polyethylene, polyisobutene, polyisoprene, poly-(4-methyl-1-pentene), polypropylene, ethylene-propylene copolymer, ethylene-propylene-hexadiene multipolymer and vinyl-vinyl acetate copolymer; Styrene polymer, for example polystyrene, poly-(2-methyl styrene); Vinyl polymer, for example poly-vinyl butyrate, poly-capric acid vinyl acetate, poly-laurostearic acid vinyl acetate, poly-palmitic acid vinyl acetate, poly-vinyl caproate, polyvinyl proprionate, poly-sad vinyl acetate; Acrylate copolymer, for example poly-n-butyl acetate, polyethyl acrylate, Vinalac 5920, polyisobutyl methacrylate, polymethyl tert-butyl acrylate, polymethyl acrylic acid dodecane ester, polyethyl methacrylate, polymethyl acrylic acid 2-ethylhexyl, the just own ester of polymethyl acrylic acid, polymethyl acid phenenyl ester, poly-n-propyl methacrylate, polymethyl acrylic acid octadecane ester; And polyester, for example polyethylene terephthalate, polybutylene terephthalate and poly-to naphthalic acid second diester.Term " hydrophobic polymer " also can comprise polyhutadiene, polysulfonates, polylactone and polyethylene oxide.
Term used herein " hollow-fibre membrane " is intended to refer to have the film of the hollow kernel that is surrounded by the wall that seals.Though some hollow-fibre membranes can be the shapes of general toroidal pipe, this term should not be interpreted as expression, and hollow-fibre membrane is the ring pipe form but can has any shape of cross section.In this disclosure, the wall of hollow-fibre membrane is partly permeable at least for selected chemical classes.Therefore, physically permeable tubular fibre (for example, owing on hollow fiber walls, there is a hole) and/or chemically permeable tubular fibre (for example, because chemical classes is passed the mass transfer of hollow fiber walls) all be included within the implication of this definition.
Term used herein " oil " looks like, and comprises chemistry or the biosynthetic oil and the mineral oil of all kinds, comprises crude oil; Lubricating oil; Crude vegetable oil and the oil fuel that is used for oil engine, steam turbine, generator and well heater; Hydraulic transmission oil; Lubricating fluid; Thermal oil; Compressor oil; Lamination oil; Metal working fluids; Refrigeration oil; Edible oil; Vegetables oil; And analogue.
In the present disclosure context, term " oily raw material " is interpreted as, and refers to contain the oil of pollutent.
When using in the linguistic context at oily raw material, term " pollutent " comprises coloured contaminant and non-coloured contaminant, and they can be removed at least in part, with recovered oil and allow its use or re-use.Coloured contaminant is the pollutent that causes or impel oily variable color, includes but not limited to, what exist in combustion processes by product-carbon residue, thickened oil, metal oxide such as ferric oxide (i.e. rust) and the oil degrades or the organic additive of oxidation.Non-coloured contaminant be interpreted broadly into, comprise any non-oil ingredient, for example may be present in the oil component, and it does not influence the color of oil as the by product of its use.For example, be used at oil under the situation of oil engine, product can be dust, solid particulate, chip, metallic particles, water and the compound that may also cause smell.Exemplary pollutent comprises because the settling that metallic particles, antiwear additive, the water from engine and storage vessel, dissolved gasoline and gas oil, solvent, aromatic compound and the scavenging solution that engine scuffing or corrosion cause, external dust, the carbonaceous particles that produces because of the automotive fuel burning are formed, improve viscosity or disperse the polymeric additive of sludge, from lead and antiknock dope, antioxidant and the washing dispersing additive of gasoline.In one embodiment, main non-coloured contaminant is a dust.In some embodiments, waste oil is the inhomogeneous product from the oil of several sources collection.
As used herein, term " retention " and " oily retention " refer to not pass through the oil of hydrophobic polymer film.The oil retention can be the oil by the hydrophobic polymer film never, and perhaps it can comprise by at least one hydrophobic polymer film but at the specified phase of the process of removing pollutent from the oil oil by the hydrophobic polymer film.For example, in the method that comprises a plurality of hydrophobic polymer films that crossfire links to each other, the penetrating oil of the first hydrophobic polymer film is transported to next hydrophobic polymer film, and the oil part by next hydrophobic polymer film is not reservation oil, even it is by the first hydrophobic polymer film.
Term " recovered oil " comprises that pollutent wherein has been removed to any oil of the level that can be used or utilize, for example as the oil of internal combustion engine lubricant.
As used herein, term " purifying " and grammatical variants thereof broadly are interpreted as, and refer to that oil has experienced method as herein described, so that oil base originally do not contain above-mentioned coloured contaminant and non-coloured contaminant.
When this paper uses, term " rate of recovery " refers to, the ratio of the initial oily raw material volume of charging in the penetrating oil volume that produces in disclosed method and the method.
In the context of the present specification, the ratio of " packing fraction " total surface area of referring to film and total membrane volume.
Word " basically " is not comprise " fully ", and for example " basically " composition of not containing Y can not contain Y fully.If desired, word " basically " can omit from definition of the present invention.
Except as otherwise noted, term " comprises " and grammatical variants, is intended to expression " open " or " comprising property " language, and they comprise described key element like this, but also allow to comprise key element other, that do not address.
As used herein, in the linguistic context of formulation concentration of component, term " approximately " is often referred to described numerical value+/-5%, more generally refer to described numerical value+/-4%, more generally refer to described numerical value+/-3%, more generally refer to described numerical value+/-2%, even more generally refer to described numerical value+/-1% and even more generally refer to described numerical value+/-0.5%.
In disclosure in the whole text, some embodiment is open with range format.The description that should be appreciated that range format should not be construed as the fixed constraints to disclosed scope only for convenience with succinct.Therefore, the description of scope should be counted as, and contains the single numerical value in concrete disclosed all possible inferior scope and this scope.For example, the range describe such as 1 to 6 should be counted as containing concrete disclosed inferior scope, and for example 1 to 3,1 to 4,1 to 5,2 to 4,2 to 6,3 to 6 etc., and the single numerical value of this scope, for example 1,2,3,4,5 and 6.Regardless of the scope width, this all is suitable for.
Summary of the invention
Describe now and remove exemplary, the non-limiting embodiment of the method for pollutent by permeable hydrophobic polymer film.The method of removing pollutent from oil comprises step: make oily raw material by permeable hydrophobic polymer film, have the still less penetrating oil of pollutent to form with respect to described oily raw material.
In one embodiment, provide a kind of method of from oil, removing pollutent, may further comprise the steps:
Provide the oily raw material that contains pollutent in enclosed slot;
Provide a plurality of permeable hydrophobic hollow-fibre membranes in described enclosed slot;
Apply pressure to described permeable hydrophobic hollow-fibre membrane; With
Make to the described oily raw material of small part by described permeable hydrophobic hollow-fibre membrane, in the chamber of described permeable hydrophobic hollow-fibre membrane, form and have the still less penetrating oil of pollutent with respect to described oily raw material.The described step that applies can comprise step: apply the described chamber side of negative pressure to described hollow-fibre membrane, apply charging one side that just is being pressed onto described hollow-fibre membrane simultaneously.Advantageously, bonded malleation and negative pressure provide motivating force, make oil have more high-throughput, and by described film, all described pollutents are able to remove from described oil so basically.
In one embodiment, the malleation that is applied to described film charging one side can be that about 0.2 crust (20kPa) is to about 5 crust (500kPa); About 0.2 crust (20kPa) is to about 4 crust (400kPa); About 0.2 crust (20kPa) is to about 3 crust (300kPa); About 0.2 crust (20kPa) is to about 2 crust (200kPa); About 0.2 crust (20kPa) is to about 1 crust (100kPa); About 0.2 crust (20kPa) is to about 0.5 crust (50kPa); About 0.8 crust (80kPa) is to about 5 crust (500kPa); About 1.2 crust (120kPa) are to about 5 crust (500kPa); About 1.8 crust (180kPa) are to about 5 crust (500kPa); About 2 crust (200kPa) are to about 5 crust (500kPa); About 3 crust (300kPa) are to about 5 crust (500kPa); About 3.5 crust (350kPa) are to about 5 crust (500kPa); And about 4 crust (400kPa) are to about 5 crust (500kPa).
In one embodiment, provide a kind of method of from oil, removing pollutent, further comprise step: make described penetrating oil by described or another permeable hydrophobic polymer film, from described oil, removed up to described pollutent basically.
In one embodiment, hydrophobic polymer can be selected from polyolefine, acrylate copolymer, vinyl polymer, polyester, lactone polymer, siloxane polymer, pyridine polymers, carbonate polymer.
In one embodiment, hydrophobic polymer can comprise two or more polymkeric substance and the random copolymers that made by two or more different monomers and the adulterant of segmented copolymer.
Exemplary polyolefine can comprise polyethylene, polypropylene, poly-(1-butylene), poly-(2-butylene), poly-(1-amylene), poly-(2-amylene), poly-(3-Methyl-1-pentene), poly-(4-methyl-1-pentene), poly-(iso-butylene), poly-(second propylene), their derivative, salt and combination.In preferred embodiment, polyolefine can comprise polyethylene and polypropylene.
Exemplary acrylate copolymer can comprise polyacrylic acid alkane ester, for example polyethyl acrylate, Vinalac 5920, polyisobutyl methacrylate, polymethyl tert-butyl acrylate, polymethyl acrylic acid dodecane ester, polyethyl methacrylate, polymethyl acrylic acid 2-ethylhexyl, the just own ester of polymethyl acrylic acid, polymethyl acid phenenyl ester, poly-n-propyl methacrylate, polymethyl acrylic acid octadecane ester, their derivative, salt and combination.
Exemplary vinyl polymer can comprise polyvinyl acetate, polystyrene, poly-vinyl butyrate, poly-capric acid vinyl acetate, poly-laurostearic acid vinyl acetate, poly-palmitic acid vinyl acetate, poly-vinyl caproate, polyvinyl proprionate, poly-sad vinyl acetate, their derivative, salt and combination.
Exemplary polyester can comprise polyethylene terephthalate, polybutylene terephthalate and poly-to naphthalic acid second diester, their derivative, salt and combination.
Exemplary siloxane polymer can comprise polysiloxane, polydimethylsiloxane and PSI, their derivative, salt and combination.
Exemplary pyridine polymers can comprise polypyridine, poly-dipyridyl, poly-terpyridyl, poly-phenanthroline and their derivative, salt and combination.
Exemplary carbonic ether can comprise annular carbonate polymer, for example the Copolycarbonate of the polycarbonate of dihydroxyphenyl propane, dihydroxyphenyl propane, homo-polycarbonate and their derivative, salt and combination.
Advantageously, can select the hydrophobic porous film, allowing to have only a small amount of or not have the oil infiltration of pollutent to pass, described pollutent comprises that water, coloured contaminant and the infiltration of non-coloured contaminant pass.This can form and mainly contain the particularly retention of water of pollutent, and it can not penetrate film.
Advantageously, permeable hydrophobic membrane allows described oily raw material to pass through, and gets rid of the water in the described oily raw material substantially, makes described water base to remove from described reservation oil.
In one embodiment, permeable hydrophobic polymer film comprises hydrophobic grouping, and it can be selected from alkyl, is preferably low-carbon alkyl, alkylidene group, is preferably low-carbon (LC) alkylidene group and thiazolinyl, is preferably the low-carbon (LC) thiazolinyl.
In one embodiment, permeable hydrophobic polymer film can be selected from hollow-fibre membrane, spiral stretch film, tubular film and capillary membranes.In one embodiment, permeable hydrophobic polymer film is the tubular fibre form membrane.
In one embodiment, provide a plurality of described hollow-fibre membranes, use in the method.
In another embodiment, at least one permeable hydrophobic polymer film can comprise internal diameter and external diameter.The internal diameter of described permeable hydrophobic polymer film can be to be selected from about scope of 0.1 to about 5mm.Therefore, in another embodiment, the internal diameter of described permeable hydrophobic polymer film can be 0.2-1mm.The external diameter of described hollow-fibre membrane can be to be selected from about scope of 0.2 to about 7mm.Therefore, in another embodiment, the external diameter of described permeable hydrophobic polymer film can be 0.3-1.5mm.
In one embodiment, the aperture of described permeable hydrophobic polymer film can be to be selected from following scope: about 0.001 μ m is to about 10 μ m; About 0.001 μ m is to about 8 μ m; About 0.001 μ m is to about 6 μ m; About 0.001 μ m is to about 4 μ m; About 0.001 μ m is to about 2 μ m; About 0.001 μ m is to about 1 μ m; About 0.005 μ m is to about 10 μ m; About 0.025 μ m is to about 10 μ m; About 0.125 μ m is to about 10 μ m; About 0.25 μ m is to about 10 μ m; About 0.2 μ m is to about 10 μ m; And about 0.1 μ m is to about 10 μ m.Therefore, in one embodiment, the aperture of described permeable hydrophobic polymer film is the scope of about 0.05 μ m to about 5 μ m.In another preferred embodiment, the aperture of described film is that about 0.01 μ m is to about 1 μ m.
In one embodiment, the porosity of described permeable hydrophobic polymer film can be selected from following scope: about 20% to about 80%; About 20% to about 65%; About 20% to about 50%; About 20% to about 35%; About 35% to about 80%; About 50% to about 80%; And about 65% to about 80%.Therefore, in one embodiment, the porosity of described film is about 30% to about 60%.
Make described oily raw material by described permeable hydrophobic polymer film so that in the step that described pollutent is removed from described oily raw material, the coloured contaminant that exists in the described oily raw material can be from the two kinds of sources that can be removed by described film.First kind of color source can be from the carbon residue, and it can exist with very thin particle, and the organic additive and the metal oxide of autoxidizable oil, degraded can be come in second kind of color source.Be not subject to theory, carbon granule may not pass through film, and big by the aperture because they may be than film, this can guarantee that they remove from described oily raw material.The oil of oxidation, the organic additive of degraded and metal oxide can be attracted on the thin nonpolar particle, for example may be present in that thin natural gum, wax in the oily feedstream drips, the degradant additive of copolymerization, and can come out with retention, make them from described penetrating oil, to remove to small part.
In one embodiment, at least one can be immersed in the oil phase basically in described a plurality of permeable hydrophobic hollow-fibre membrane.In another embodiment, provide the enclosed slot that wherein contains described oily raw material, wherein said a plurality of permeable hydrophobic hollow-fibre membranes can be immersed in the described groove basically.This embodiment can comprise, the chamber side that oily raw material enters fiber from the outer wall of hollow-fibre membrane forms penetrating oil.In one embodiment, at least one of described groove gone into interruption-forming oil feedstream, so that described oily raw material is introduced described groove.
In one embodiment, a plurality of permeable hydrophobic hollow-fibre membranes are installed in the film module, and this module comprises the framework that holds film is set.This module can be placed in the enclosed slot.Module can be the form of tube, and it has the permeable closure wall that is used to insert oily raw material tank.Module can have at least one outlet, to form penetrating oil stream, described penetrating oil is collected in the hold tank.
In one embodiment, the negative pressure that is applied to the chamber side of described hollow-fibre membrane (10kPa) extremely-1.0 is clung to (100kPa) for-0.10 crust.In one embodiment, this negative pressure is following scope: less than approximately-0.1 clinging to (10kPa); Less than approximately-0.5 clinging to (50kPa); Less than approximately-1 clinging to (100kPa).
Advantageously, the low relatively operation negative pressure that puts on described permeable hydrophobic polymer film produces much lower energy consumption, and stops described oil making described oily raw material oxidized in the step by described hollow-fibre membrane.Under vacuum condition, oil contacts with little air, or does not contact with air, and therefore the oxidation of oil is avoided or alleviated at least.Therefore, subnormal ambient stops the quality of described penetrating oil to reduce because of oxidation.
In one embodiment, service temperature is in following ranges: about 10 ℃ to about 90 ℃; About 10 ℃ to about 70 ℃; About 10 ℃ to about 60 ℃; About 10 ℃ to about 50 ℃; About 10 ℃ to about 40 ℃; About 10 ℃ to about 30 ℃; About 30 ℃ to about 70 ℃; About 35 ℃ to about 70 ℃; About 40 ℃ to about 70 ℃; About 45 ℃ to about 70 ℃; About 50 ℃ to about 70 ℃; About 55 ℃ to about 70 ℃; About 60 ℃ to about 70 ℃; And about 65 ℃ to about 70 ℃.
Advantageously, low operating temperature stops described oil oxidized in making the step of described oily raw material by described hollow-fibre membrane.In this respect, if adopt High Operating Temperature, then oil may be oxidized easily, and this may make the color blackening of described penetrating oil, and therefore reduced the quality of described penetrating oil.The big film " packing fraction " of further described hollow-fibre membrane allows described method to operate at low temperatures and can not cause the oxidation of described oil.
Advantageously, high film packing fraction can be offset the defective of small throughput.Small throughput is due to the fact that and causes: do not use solvent to reduce oil viscosity, and also be the result of cold operation.In this way, keep conventional flow velocity and throughput.Further, for the film of other type, can not obtain so high film packing fraction.And, use mineral membrane to obtain the cost of same throughput rate with much higher.In one embodiment, passing the flux that described permeable hydrophobic polymer film produces can be to be selected from following scope: about 0.004L/m
2/ h is to about 5L/m
2/ h; About 0.004L/m
2/ h is to about 2.5L/m
2/ h; About 0.004L/m
2/ h is to about 1L/m
2/ h; About 0.008L/m
2/ h is to about 5L/m
2/ h; About 0.01L/m
2/ h is to about 5L/m
2/ h; About 0.02L/m
2/ h is to about 5L/m
2/ h; About 0.05L/m
2/ h is to about 5L/m
2/ h; About 0.08L/m
2/ h is to about 5L/m
2/ h; About 0.1L/m
2/ h is to about 5L/m
2/ h; About 0.25L/m
2/ h is to about 5L/m
2/ h; About 0.5L/m
2/ h is to about 5L/m
2/ h; With about 1L/m
2/ h is to about 5L/m
2/ h; About 1.5L/m
2/ h is to about 5L/m
2/ h; And about 2.5L/m
2/ h is to about 5L/m
2/ h.In preferred embodiment, the flux that passes described permeable hydrophobic polymer film generation can be about 0.02L/m
2/ h is to about 2.0L/m
2The scope of/h.
In another embodiment, permeable hydrophobic polymer film device can be operated under barotropic model.This embodiment can comprise a plurality of described hollow-fibre membranes, and its lumen forms charging one side, and the outside of film forms penetrant one side, described film go into interruption-forming oil feed(raw material)inlet, the discharging current that goes out the described film of interruption-forming of film.On the contrary, in comprising the embodiment of a plurality of hollow-fibre membranes, the chamber can form per-meate side, and the outside of described film forms feeding side.
In one embodiment, provide the method for from oil, removing pollutent, further comprise step: remove the oil that does not pass through permeable hydrophobic polymer film.In another embodiment, at least a portion of described oily retention turns back to oily feedstream.
In one embodiment, be provided at the method for purifying oil in the oily purification system, this system comprises at least one hydrophobic polymer film, this film a lateral confinement stand oil raw material of film zone and with isolating penetrating oil zone, described oily raw material zone, said method comprising the steps of:
(a) the oily raw material that will wherein contain pollutent is fed to oily raw material zone;
(b) apply pressure to described film;
(c) make to the described stock oil of small part by described film, to form penetrating oil in described penetrating oil zone;
(d), remove to small part and to keep oil from oily raw material zone;
(e) make described penetrating oil enter described oily raw material zone; With
(f) repeating step (c) is removed from described penetrating oil up to all basically described pollutents to (e).In one embodiment, the penetrating oil zone comprises a plurality of closed regions of the independent enclosed slot that is arranged in a plurality of membrane separation apparatuss.
In one embodiment, oily raw material has the still less penetrating oil of pollutent to produce continuously with respect to described oily raw material continuously by a plurality of permeable hydrophobic hollow-fibre membranes in the chamber of described film.Advantageously, oily retention can be recycled to oily feedstream, to be further purified, improves the oil recovery rate.Therefore, described oily raw material continuously feeding can improve the Pollutant levels of described oily retention in the groove by film.Advantageously, the oil recovery rate that obtains from described method is improved.Therefore, the viscosity of described oily retention improves, and strides across the flux decline that described film produces.When oil recovery rate for example reached 70% to 85% level, oily retention dense in the described groove was emitted, and can further be produced and be oil fuel.
Back scrubbing
This method can comprise step: makes the relatively high pressure fluid by the film surface discontinuously, perhaps passes film, and may plugging hole or besmirch the material on film surface to remove.Advantageously, should " back scrubbing " step keep the processing property of film in its length of life.
Used relatively high pressure fluid can be a pressurized air.In another embodiment, high pressure fluid can be the rare gas element of compression.Rare gas element can be selected from nitrogen, argon, helium and carbonic acid gas.The typical high pressure fluid that is used to dredge film can be a following ranges: greater than 0 crust (0kPa) to about 5 crust (500kPa); With extremely about 5 crust (500kPa) of about 4 crust (400kPa).In preferred embodiment, the high pressure fluid that is used to dredge film can be that about 1 crust (100kPa) is to about 3 crust (300kPa).
In backwash process, gas can not enter feeding side by described film.Gas provides all the described penetrating oils basically in the chamber that makes hollow-fibre membrane to enter the pressure of the described feeding side of film.In backwash step, the penetrating oil that used relatively high pressure fluid also can film.This can form when using with film mutually that the pressure drop of ratio inverse realizes by striding across film.In backwash step, can apply penetrant one side that just is being pressed onto film, thereby force penetrant to pass through film, return the feeding side of film from penetrant one side.In backwash step, also can apply charging one side of negative pressure at film, forming vacuum at feeding side, thereby force penetrating oil to flow to the feeding side of film from per-meate side.Fluid strides across the reversed flow of film in the backwash step, compares when using with film, can remove in the fenestra or the material on surface, and this flux that has advantageously stoped film to besmirch and stride across film descends.
In another embodiment, the relatively high pressure fluid can be the low solvent of viscosity ratio penetrating oil.
Description of drawings
Description of drawings has illustrated disclosed embodiment, is used to explain the principle of disclosed embodiment.Yet, should be appreciated that accompanying drawing only is used for illustration purpose, not limitation of the invention.
Fig. 1 is to use the hydrophobic polymer film to remove the synoptic diagram of the method for pollutent from oily raw material.
Fig. 2 is the constructed profile of the employed hollow-fibre membrane of method among Fig. 1.
Fig. 3 is according to one of embodiment disclosed herein, shows flux and the time dependent figure of the rate of recovery.
Fig. 4 is according to one of embodiment disclosed herein, shows the figure that film module flux rises and descends with the rate of recovery.
Fig. 5 is according to one of embodiment disclosed herein, is presented at the time dependent figure of flux under the situation of penetrating oil back scrubbing.
Fig. 6 is according to one of embodiment disclosed herein, shows flux and the time dependent figure of the rate of recovery.
Fig. 7 shows that flux improves the figure that descends with the rate of recovery.
Embodiment
Fig. 1 shows the group method 100 of removing pollutent from useless motor oil.Method 100 is removed pollutent from oil, make it to utilize as motor oil once more again.Pump 12 is pumped into motor oil the enclosed slot of film jar 14 forms from motor oil feedstream 10.Jar 14 holds film module (A, B, C, D, E, F).Each film module A-F forms (see figure 2) by the annular porose casing that a plurality of hollow fiber film tubes 203 wherein are installed (200A, 200B, 200C, 200D, 200E, 200F).
Fig. 2 shows the part amplification fish-eye view of one of hollow fiber film tube 203.Pipe 203 has outer feeding side 202 and interior per-meate side 204.As further describing below, between the usage period, keep negative pressure in interior per-meate side 204, the useless motor oil 212 of feeding side 202 penetrates the wall of pipe 203 outside, forms penetrating oil 214.Therefore pollutent in the waste oil for example dust is stayed in the oily retention of outer feeding side 202 not by pipe 203.The upper end (not shown) of film pipe is connected with permeate line 16 by the permeable tank (not shown), and permeable tank is positioned at film module A-F top, and penetrant is collected therein.
Referring to Fig. 1, the film module A-F that comprises film pipe 203 almost completely is immersed in the useless motor oil 212 once more.Surge pump 18 provides negative pressure to pipe 203, and this makes penetrating oil 214 be collected in the permeate conduit of each film module A-F, discharges by pipeline 16 then, and is collected in the penetrating oil hold tank 20.Oil in the jar 20 has been removed non-coloured contaminant, still stays in the penetrating oil yet have some coloured contaminants that are not removed.In order to remove these coloured contaminants, can use Fuller's earth absorption coloured contaminant.
The circulation line 22 that comprises recycle pump 24 and interchanger 26 also is connected to film jar 14.By this process, keep oil and be pumped membrane jar 14 and enter film jar 14 again by interchanger 26.This working cycle guarantees to keep turbulent flow and oily 212 constant temperature in film jar 14.
In the use, pollutent may besmirch the surface of film pipe 203.In order to remove or the dirt on the partial regeneration film pipe 203 at least, carry out backwash process discontinuously.During backwash process, the direction of penetrating oil 214 is anti-because the penetrating oil that exists in jars 20 is by surge pump 18 and pipeline 21 return tubes 203, and outside interior per-meate side 204 enters feeding side 202.This backwash process can be removed the pollutent in the tubular fibre fenestra.
Because more penetrating oil leaves film jar 14 by permeate line 16, therefore the concentration of pollutent increases in the oil 212.In case reach the predetermined rate of recovery as 85%, just be released to and concentrate in the oil tank 28 with spissated oily 212.
Embodiment
By referring to specific embodiment, non-limiting example of the present invention, the scope that it should be construed as limiting the invention by any way will be described in more detail further.The method of testing below is the same procedure 100 referring to above-mentioned Fig. 1, also mentions similar square law device operation below.Below in all experiments oily raw material be the useless motor oil of blended, obtain from the waste oil gathering station that is positioned at Singapore.Therefore, this useless motor oil is the adulterant of useless motor oil, and it is formed and character is listed as " stock oil " hurdle in the following Table 1.
Below the hydrophobic porous polymeric film that uses in all experiments be to derive from polyolefinic organic hollow tunica fibrosa, aperture 0.03 μ m, interior external diameter is respectively 0.325mm and 0.45mm.The film tank volume is 3m
3, 56 hollow fiber film tubes 203 wherein are housed.Therefore, comprise hollow-fibre membrane the jar in total membrane area be 2240m
2
Unless point out in addition in each specific embodiment, the negative pressure of permeate line is provided by surge pump 18, and remains on the scope of-0.5 to-0.6 crust.
Embodiment 1
In this embodiment, useless motor oil keeps 50 ℃ temperature and operation continuously, interrupts 1 hour after per 11 hours.Intercourse at 1 hour, the surge pump 18 on the permeate line 16 cuts out, and leaves standstill for some time to allow film.
The circulating rate and the rate of recovery show in Fig. 3 that over time the pass between the circulating rate and the rate of recovery ties up among Fig. 4 and shows.
From Fig. 3 and Fig. 4 as seen, flux descends linearly with the rising of the rate of recovery substantially.Also as seen, flux rises after film leaves standstill for some time, shown in data line R1, R2, R3, R4, R5, R6.
In the operate continuously process of system 100, on the surface of membrane fiber, form the oil that one deck has viscosity higher and higher pollutant load.This has stoped oil by film, has influenced flux unfriendly.During film left standstill, vacuum pump cut out, but recycle pump stays open.Thicker oil reservoir is loosened and is recycled stream and cleaned on the film surface.Therefore, the oil viscosity around the membrane fiber descends, and makes that flux increases when turning round once more in system.This shows, is fit to keep higher relatively membrane flux during film leaves standstill.
Embodiment 2
In this embodiment, useless motor oil remains on 32-34 degree centigrade and also moves 12 hours every day.The method that is used for the regeneration membrane flux is by oily back scrubbing.
When flux drops to below the 0.02LMH, carry out the penetrating oil back scrubbing, with the flux of regeneration membrane.In this process, under pressure+1.5 crust, penetrating oil is pumped through film from the per-meate side of film.The oil back scrubbing was carried out 30 minutes at every turn.
The circulating rate and the rate of recovery show in Fig. 5 over time.As seen, flow rate increases in time, and the rate of recovery descends.Also as seen, flow rate increases after the penetrating oil back scrubbing, shows that oily back scrubbing is suitable for keeping higher relatively membrane flux.
But penetrating oil be used and be consumed to oily back scrubbing need, is uneconomic.And process is in a segment length time, and average production rate will descend.
Embodiment 3
In this embodiment, useless motor oil remains on 50 ℃ and operate continuouslys, in conjunction with the film regeneration of carrying out 30 fens clock times after per 5.5 hours.At the film regeneration period, carry out oily back scrubbing 10 minutes, be during 20 minutes film leaves standstill then.
The circulating rate and the rate of recovery show in Fig. 6 that over time the pass between the flow rate and the rate of recovery ties up among Fig. 7 and shows.
Bonded film renovation process has shown good performance because it combine oily back scrubbing and film leave standstill during the two advantage.The oily back scrubbing of short period consumes less penetrating oil, has removed the pollutent that stops up fenestra simultaneously, and film leaves standstill for some time, makes to have reducing than thick oil pay of viscosity higher and higher pollutant load around the film surface.
The result is that this bonded method demonstrates than the much better performance of arbitrary method itself.
Embodiment 4
In this embodiment, useless motor oil remains on 32-35 degree centigrade and turn round, and negative pressure remains on-300 millibars to-550 millibars.Operation is after 1 hour and 24 hours continuously in system, and the sample of collection penetrating oil obtains RBO (recovery base oil) sample in 12% clay bleaching test back.
The character of raw material waste oil, penetrating oil and RBO shows in the following Table 1.As seen, the outward appearance of refiltered oil, color and amount of pollutants are compared remarkable improvement with waste oil.For example, the color of product oil (RBO: reclaim base oil) can be less than colour code 3 after the clay bleaching.In addition, because the hydrophobic property of film, water can be removed effectively.Water-content can be less than 0.03% in the penetrating oil.
Table 1: the characteristic of raw material waste oil, penetrating oil and RBO
Use
Advantageously, use permeable hydrophobic polymer film disclosed herein to cause from oil, having removed in a large number pollutent such as coloured pollutent and non-coloured contaminant.Therefore, disclosed method can be used for from from various industry for example the waste oil of ocean, petroleum chemistry, mining, steel mill, machinery, electric power, automobile, building and aircraft industry remove pollutent.Therefore, You normal use is unaffected.
Advantageously, disclosed method allows oily recirculation, causes oil recovery to increase.Therefore, disclosed method helps to reduce Waste-oil combustion and discarded incident, thereby reduces the pollution problem relevant with waste oil treatment.
Advantageously, disclosed method causes high relatively recovery of oil.Therefore, disclosed method provides the effective ways of removing pollutent from oil.
Advantageously, method disclosed herein does not need to use any solvent or chemical substance that is used for oil dilution or purifying.Therefore, method as herein described is safe to environment, because this method can overcome and the known relevant problem of acid treatment that is used to remove oil contaminants, thereby has avoided the generation of very poisonous sour sludge.
Further, disclosed method does not need to use evaporation or the distillating method that utilizes thin-film evaporator.Therefore, disclosed method has been avoided the problem relevant with the coking effect, and this coking acts in these known methods and often causes besmirching vaporizer.
Disclosed method does not need to use any solvent to come thinning oil to be beneficial to filtration to reduce oil viscosity.Therefore, disclosed method does not consume any solvent, thereby has reduced the noxious emission of solvent.
Disclosed method need not carried out under condition of high voltage.And the method for the disclosure is carried out at low temperatures effectively, so it has reduced the generation of the oily oxidation of the quality that can influence oil.Therefore, the method for the disclosure is fit to produce highly refined oil economically, and does not need high energy consumption.
The method of the disclosure is used hydrophobic membrane, and it is more relatively cheap than known mineral membrane.Permeable hydrophobic polymer film disclosed herein can remove any water that exists in the raw material that deoils basically, makes water be removed substantially from penetrating oil.Therefore, the hydrophobic polymer film has stoped the pollutent that comprises water to enter described penetrating oil by film.Therefore, because the oil of film repels characteristic, the method for the disclosure does not need further dewatering unit to come except that the water in deoiling.
Advantageously, high film packing fraction can be offset the defective of small throughput, and allows to keep the flow velocity or the throughput of routine, and does not use solvent and High Operating Temperature.
Significantly, various other modification of the present invention and variation are to those skilled in the art, after having read above-mentioned disclosure, be obvious, and can not deviate from the spirit and scope of the present invention that all these modification and variation are all within the scope of the appended claims.For example, reach oil handling though disclosed embodiment has been described knacker particularly, it will be appreciated that in other embodiments, this method can be used for removing coloured contaminant and non-coloured contaminant from crude oil or part treated oil.
Claims (33)
1. method of removing pollutent from oil comprises step:
(a) make oily raw material by permeable hydrophobic polymer film, formation has the still less penetrating oil of pollutent with respect to described oily raw material.
2. the described method of claim 1 comprises step:
(b) make described penetrating oil by described or another permeable hydrophobic polymer film.
3. the described method of claim 2 comprises step:
(c) repeating step (b) is removed from described oil up to all basically described pollutents.
4. the described method of claim 1 comprises step:
(d) amount that non-Oil solvent is provided is by volume less than about 20% described oily raw material.
5. the described method of claim 4 comprises step:
(e) provide the described oily raw material that is substantially free of non-Oil solvent.
6. the described method of claim 1, wherein said hydrophobic polymer film is the tubular fibre form membrane.
7. the described method of claim 6, wherein a plurality of hollow-fibre membranes are configured in the enclosed slot that comprises described oily raw material.
8. the described method of claim 1, wherein said hydrophobic polymer is selected from polyolefine, acrylate copolymer, vinyl polymer, polyester, lactone polymer, siloxane polymer, pyridine polymers, fluoropolymer and carbonate polymer.
9. the described method of claim 1, the aperture of wherein said permeable hydrophobic polymer film is in the scope of 0.001 μ m to about 10 μ m.
10. the described method of claim 1, the porosity of wherein said permeable hydrophobic polymer film is in 20% to 80% scope.
11. the described method of claim 1 comprises step:
(f) apply pressure to described film.
12. the described method of claim 11 wherein applies step (f) and may further comprise the steps:
(f1) apply penetrant one side of negative pressure to described film; With
(f2) apply charging one side that just is pressed onto described film.
13. the described method of claim 12, wherein said apply step (f1) and apply step (f2) apply for some time simultaneously.
14. claim 12 or 13 described methods, wherein said film comprises a plurality of hollow-fibre membranes, and wherein saidly applies the chamber side that step (f1) is applied to described tubular fibre, applies wall one side that step (f2) is applied to described tubular fibre simultaneously.
15. the described method of claim 12, wherein in the described step (f1) that applies, described negative pressure (10kPa) extremely-1 is clung to (gauge pressure scope 100kPa) at-0.1 crust.
16. the described method of claim 12, wherein in the described step (f2) that applies, described malleation is clung to (20kPa) to 5 crust (500kPa) scopes 0.2.
17. the described method of claim 1 is wherein carried out to the temperature of 90 ℃ of scopes at 10 ℃ by step (a).
18. the described method of claim 1 comprises step:
(h) described in continuation by before the step, stop described discontinuously by step (a) for some time.
19. the described method of claim 1 comprises step:
(i) stop to make oily raw material by described film; With
(j) make oily charging one side that enters described film except the fluid of described oily raw material from penetrant one side.
20. the described method of claim 19, wherein said fluid are penetrating oil.
21. the described method of claim 19, wherein said fluid are the solvent that viscosity is lower than described penetrating oil.
22. the described method of claim 7 comprises step:
(k) described a plurality of hollow-fibre membrane is immersed in the described oily raw material that disposes in the described enclosed slot.
23. a method of removing pollutent from oil may further comprise the steps:
(a) provide contain pollutent oily raw material in enclosed slot;
(b) provide a plurality of permeable hydrophobic hollow-fibre membranes in described enclosed slot;
(c) apply pressure to described permeable hydrophobic hollow-fibre membrane; With
(d) make to the described oily raw material of small part by described permeable hydrophobic hollow-fibre membrane, in the chamber of described permeable hydrophobic hollow-fibre membrane, form and have the still less penetrating oil of pollutent with respect to described oily raw material.
24. the described method of claim 23 wherein applies step (c) and may further comprise the steps:
(c1) apply penetrant one side of negative pressure to described film; With
(c2) apply charging one side that just is pressed onto described film.
25. the described method of claim 24, wherein said apply step (c1) and apply step (c2) apply for some time simultaneously.
26. claim 24 or 25 described methods, wherein said film comprises a plurality of hollow-fibre membranes, and wherein saidly applies the chamber side that step (c1) is applied to described tubular fibre, applies wall one side that step (c2) is applied to described tubular fibre simultaneously.
27. the method for purifying oil in oily purification system, this system comprise at least one hydrophobic polymer membrane element, this element define film one side oily raw material zone and with the penetrating oil zone that described oily raw material zone separates, said method comprising the steps of:
(a) the oily raw material that will contain pollutent is fed to described oily raw material zone;
(b) exert pressure to described film;
(c) make to the described oily raw material of small part by described film, to form penetrating oil in described penetrating oil zone;
(d), remove to small part and to keep oil from described oily raw material zone;
(e) make described penetrating oil enter described oily raw material zone; With
(f) repeating step (c) is removed from described penetrating oil up to all basically described pollutents to (e).
28. the described method of claim 27 wherein applies step (b) and may further comprise the steps:
(b1) apply the permeate side of negative pressure to described film; With
(b2) apply the feeding side that just is pressed onto described film.
29. the described method of claim 28, wherein said apply step (b1) and apply step (b2) apply for some time simultaneously.
30. claim 28 or 29 described methods, wherein said film comprises a plurality of hollow-fibre membranes, and wherein saidly applies the chamber side that step (b1) is applied to described tubular fibre, applies wall one side that step (b2) is applied to described tubular fibre simultaneously.
31. the described method of claim 27, wherein said penetrating oil zone comprises a plurality of closed regions of the independent enclosed slot that is arranged in a plurality of membrane separation apparatuss.
32. an oily purification system, it comprises:
Enclosed slot is used for holding therein oily raw material;
A plurality of permeable hydrophobic hollow-fibre membranes, it is installed in the described enclosed slot so that be immersed in substantially in the described oil;
Positive pressure source, it is communicated with the wall side liquid of described hollow-fibre membrane; With
Negative pressure source, it is communicated with the chamber side liquid of described hollow-fibre membrane, to be driven in the chamber that the described oily raw material of small part enters described film and to produce penetrating oil therein.
33. a motor oil, it is by the waste oil manufacturing according to purifying in each described method in the claim 1 to 31.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US98772207P | 2007-11-13 | 2007-11-13 | |
| US60/987,722 | 2007-11-13 |
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| CN101434858A true CN101434858A (en) | 2009-05-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2008101752927A Pending CN101434858A (en) | 2007-11-13 | 2008-11-13 | Method for removing pollutant in oil |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102462977A (en) * | 2010-11-19 | 2012-05-23 | 北京仁创科技集团有限公司 | Oil-water separation device and floating oil collection system with oil-water separation device |
| CN105295987A (en) * | 2015-10-19 | 2016-02-03 | 长江大学 | Method for removing oil extraction polymer from crude oil |
-
2008
- 2008-11-13 CN CNA2008101752927A patent/CN101434858A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102462977A (en) * | 2010-11-19 | 2012-05-23 | 北京仁创科技集团有限公司 | Oil-water separation device and floating oil collection system with oil-water separation device |
| CN102462977B (en) * | 2010-11-19 | 2014-09-10 | 北京仁创科技集团有限公司 | Oil-water separation device and floating oil collection system with oil-water separation device |
| CN105295987A (en) * | 2015-10-19 | 2016-02-03 | 长江大学 | Method for removing oil extraction polymer from crude oil |
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Open date: 20090520 |