CN107286973A - The preparation method of oily recovery method and lube base oil in spent bleaching clay - Google Patents
The preparation method of oily recovery method and lube base oil in spent bleaching clay Download PDFInfo
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- CN107286973A CN107286973A CN201610202114.3A CN201610202114A CN107286973A CN 107286973 A CN107286973 A CN 107286973A CN 201610202114 A CN201610202114 A CN 201610202114A CN 107286973 A CN107286973 A CN 107286973A
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- bleaching clay
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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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
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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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/28—Recovery of used solvent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to petrochemical industry, the preparation method of recovery method oily in spent bleaching clay and lube base oil is disclosed, the recovery method includes：Under the first contact conditions, by pending spent bleaching clay and organic solvent exposure, to be desorbed the lube base oil in spent bleaching clay, under the second contact conditions, spent bleaching clay and organic solvent exposure will be handled for the first time, to dissolve the undesirable components in spent bleaching clay, under the 3rd contact conditions, after-treatment spent bleaching clay is contacted with water, to dissolve the organic solvent in spent bleaching clay, organic solvent used comes from the extraction solvent that solvent refining is carried out to feedstock oil in the first contact and the second contact；First, which separate obtained oil-containing solvent mixture, returns, and is used as a part for the extraction solvent of solvent refining；Second, which separate obtained oil-containing solutions, returns, and is used as a part for feedstock oil.The method of the present invention can realize the lube base oil effectively reclaimed in spent bleaching clay.
Description
Technical field
The present invention relates to a kind of processing of clay finishing spent bleaching clay in production of lube base oils
Method, in particular it relates to recovery method oily in a kind of spent bleaching clay and the preparation side of lube base oil
Method.
Background technology
The properties such as color, oxidation stability and viscosity temperature characteristic in order to improve lube base oil will be, it is necessary to will
Undesirable components removing in lube base oil raw materials for production, retaining color is shallow, oxidation stability and viscous
The good ideal composition of warm nature energy.Ideal composition is mainly isoparaffin, the cycloalkane and virtue of the long side chain of few ring
Hydrocarbon, undesirable components are mainly polycyclic short-side chain aromatic hydrocarbons and heteroatomic compound etc..At present mainly using molten
The methods such as agent is refined, hydrotreating improve the property of lube base oil raw materials for production.Wherein, at hydrogenation
Reason is in the presence of catalyst and hydrogen, and polycyclic aromatic hydrocarbon hydrogenation saturation and open loop convert undesirable components
For ideal composition.And solvent refining by solvent to different component selective dissolution ability in feedstock oil
Purpose that is different and reaching removing undesirable components.The oil product obtained through solvent refining and/or hydrotreating is adopted
The pour point of product is reduced with methods such as catalytic dewaxing, isomerization-visbreaking or solvent dewaxings, low solidifying oil product is obtained.
The conventional lubrication oil base oil technological process of production includes solvent refining, solvent dewaxing and post-refining work
Skill step, first solvent refining, rear solvent dewaxing are referred to as positive sequence technological process, and dewaxed oil is obtained through post-refining
To lube base oil；First solvent dewaxing, rear solvent refining are referred to as inverted sequence technological process, and refined oil is through mending
Fill and be refining to obtain lube base oil.Solvent refining is because having the spies such as production cost is low, adaptability to raw material is good
Point, is applied widely in production of lube base oils.Extraction solvent mainly has phenol, N-
Methyl pyrrolidone and furfural etc., at the same temperature, selection of the extraction solvent to each component in feedstock oil
Property solvability is descending is followed successively by polycyclic aromatic hydrocarbon, few PAH, cycloalkane, isoparaffin and alkane.
Industrially, refining solvent and refined material counter current contacting in extraction tower, respectively obtain refined liquid and extraction
Liquid, recovered solvent obtains refined oil, tapped oil, recycling design and water.Containing in recycling design is water-soluble
Agent and containing aqueous solvent through aqueous solvent knockout drum, solvent seasoning tower and dehydrating tower, respectively obtain solvent recovery folder
The oil phase of band, dry solvent and water, oil phase can be made as catalytic cracking or coking raw material, dry solvent circulation
For extraction solvent, water discharge device.
The lube stock obtained through solvent refining-solvent dewaxing flow needs further post-refining, improves
The color and stability of oil product.Can be using hydrofining or the method for adsorbing post-refining.Hydrogenation
Post-refining is that under conditions of relatively relaxing, water, sulphur are hydrogenated to oxygen-containing, sulfur-bearing and nitrogen-containing compound
Change hydrogen, ammonia and hydrogenation of unsaturated hydrocarbons saturation etc. is reacted, improve the color and oxidation stability of oil product.And
Absorption post-refining is to utilize a small amount of colloid, many remained in porous, high surface area bleaching earth adsorption oil product
PAH, heteroatomic compound (sulfide, nitride and oxide) and trace solvent, moisture and
The undesirable components such as mechanical admixture, reach improvement oil product color, improve the purpose of stability.It is clay-filtered
The polar substances belonged in physical and chemical adsorption process, oil product are easily adsorbed on carclazyte duct and surface, virtue
The number of rings of hydrocarbon and cycloalkane is more high easier by bleaching earth adsorption, using the method for filtering after oil product adsorption refining
Separation of solid and liquid is carried out, lube base oil and carclazyte waste residue is obtained.The pole containing absorption is removed in carclazyte waste residue
Outside property material, a certain amount of base oil has also been adhered to.Chinese patent CN101434853B mentions spent bleaching clay
In typically contain about 30% or so oil, 2/3rds base oils for being, in addition about three points in these oil
One of be the base oils such as colloid, condensed-nuclei aromatics undesirable components, therefore reclaim spent bleaching clay in oil energy
It is enough to extract base oil component therein.
Oily recovery in spent bleaching clay first has to separate the oil in spent bleaching clay, current oil recovery
Method has the methods such as mechanical extrusion, water alkali wash and solvent extraction.Mechanical presses method is in a level pressure
Spent bleaching clay is extruded under power, oil is therefrom separated, there is the incomplete shortcoming of oil separation.Water alkali wash
It is to use clay dregs heating stirring together with a certain amount of water and alkali, oil parsing is separated, there is alkali
The problem of property wastewater treatment.Chinese patent CN101434853B is disclosed to be used for reclaiming oil plant profit
Used in the method for the refined spent bleaching clay produced of lubricating oil a kind of non-polar solven and polar solvent and it
Mixed solvent extract the oil adsorbed in spent bleaching clay, can by the lube base adsorbed in spent bleaching clay
The undesirable components such as oil and colloid, aromatic hydrocarbons are extracted completely.But, in order to obtain what is dissolved in solvent
Oil separates extraction solvent with the mixture of oil, it is necessary to individually build retracting device, there is construction and makes
The problem of using costly.
Accordingly, it would be desirable to find one kind effectively reclaims oil using solvent from oil-containing spent bleaching clay, while without
The method of newly-built solvent recovery unit.
The content of the invention
It is an object of the invention to provide recovery method and lube base oily in a kind of new spent bleaching clay
The preparation method of oil.
To achieve these goals, it is described useless the invention provides recovery method oily in a kind of spent bleaching clay
Carclazyte contains lube base oil and undesirable components, wherein, the recovery method includes：
Under the first contact conditions, by pending spent bleaching clay and organic solvent exposure, to be desorbed in spent bleaching clay
Lube base oil, and separation of solid and liquid obtains the mixture containing lube base oil and organic solvent
And spent bleaching clay is handled for the first time；
Under the second contact conditions, spent bleaching clay and organic solvent exposure will be handled for the first time, to dissolve spent bleaching clay
In undesirable components, and separation of solid and liquid obtains oil-containing solutions and after-treatment spent bleaching clay；
Under the 3rd contact conditions, after-treatment spent bleaching clay is contacted with water, to dissolve having in spent bleaching clay
Machine solvent, and separation of solid and liquid, obtain aqueous solutions of organic solvent and de-oiling spent bleaching clay；
Organic solvent used comes from molten to the progress of solvent refining feedstock oil in first contact and the second contact
The refined extraction solvent of agent；
The isolated mixture containing lube base oil and organic solvent is returned, as to molten
Agent refined material oil carries out a part for the extraction solvent of solvent refining；
The isolated oil-containing solutions are returned, and are used as a part for solvent refining feedstock oil.
Present invention also offers a kind of preparation method of lube base oil, wherein, the preparation method bag
Include：Feedstock oil is contacted into progress solvent refining with extraction solvent, refined liquid and Extract is obtained, carries out molten
Agent is reclaimed and respectively obtains refined oil, tapped oil, recycling design and water, by refined oil and dewaxing retarder thinner
Contact carries out solvent dewaxing, obtains dewaxed oil and gatch, and dewaxed oil is contacted into progress carclazyte benefit with carclazyte
Fill refined, obtain lube base oil and spent bleaching clay, the spent bleaching clay contains lube base oil and unreasonably
Think component, the preparation method also includes：
Under the first contact conditions, by pending spent bleaching clay and organic solvent exposure, to be desorbed in spent bleaching clay
Lube base oil, and separation of solid and liquid obtains the mixture containing lube base oil and organic solvent
And spent bleaching clay is handled for the first time；
Under the second contact conditions, spent bleaching clay and organic solvent exposure will be handled for the first time, to dissolve spent bleaching clay
In undesirable components, and separation of solid and liquid obtains oil-containing solutions and after-treatment spent bleaching clay；
Under the 3rd contact conditions, after-treatment spent bleaching clay is contacted with water, to dissolve having in spent bleaching clay
Machine solvent, and separation of solid and liquid, obtain aqueous solutions of organic solvent and de-oiling spent bleaching clay；
Organic solvent used comes from molten to the progress of solvent refining feedstock oil in first contact and the second contact
The refined extraction solvent of agent；
The isolated mixture containing lube base oil and organic solvent is returned, as to molten
Agent refined material oil carries out a part for the extraction solvent of solvent refining；
The isolated oil-containing solutions are returned, and are used as a part for solvent refining feedstock oil.
Oily recovery method is used in organic solvent rinsing desorption spent bleaching clay in the spent bleaching clay that the present invention is provided
Undesirable components in oil product, organic solvent dissolving spent bleaching clay, and organic solvent in water dissolving spent bleaching clay
Method and realize the recovery of oil product in spent bleaching clay, so as to obtain three kinds of products, glued respectively in spent bleaching clay
Attached most of base oil and oil-solvent mixture of organic solvent；Adsorbed in spent bleaching clay big is dissolved
The oil-containing of the undesirable components such as part colloid, heteroatomic compound are for example oxygen-containing, sulfur-bearing and nitrogen-containing compound is molten
Liquid；Dissolved organic solvent in spent bleaching clay contains aqueous solvent.Containing most of basis in above-mentioned three portion of product
Oil-solvent mixture of oil enters the extraction solvent pipeline that solvent refining is carried out to solvent refining feedstock oil,
As a part for extraction solvent, the oil-containing solutions for being dissolved with undesirable components enter to solvent refining raw material
Oil carries out the raw material oil pipeline of solvent refining, is used as a part for feedstock oil.In oil-solvent mixture
Base oil is substantially free of lube base oil undesirable components and high condensation point component, returns to solvent refining step
Afterwards, then through solvent refining, solvent dewaxing and clay-filtered flow, again as lube base oil product,
The loss that oil is adhered in spent bleaching clay is reduced, lube base oil yield is improved.It is dissolved with non-ideal
The oil-containing solutions of component are returned after solvent refining step, are entered after solvent refining in tapped oil, are improved
The yield of solvent refining byproduct.
To sum up, had the following advantages that using method oily in the recovery spent bleaching clay of the present invention：1) oil-solvent
Mixture and oil-containing solutions are respectively enterd after solvent refining unit, and solvent therein is used as refined liquid and extraction
A part in liquid, can complete solvent using the solvent recovery unit in lubricating oil solvent device and return
Receive and recycle process, without newly-built spent bleaching clay solvent recovering system.2) in oil-solvent mixture
Organic solvent enters after solvent refining unit, directly as extraction solvent, in the feelings that extracting oil ratio is constant
Under condition, part extraction solvent is substituted, does not increase solvent refining unit oil ratio.3) oil-solvent mixture
Respectively enterd with oil-containing solutions after solvent refining system, wherein the oil product in spent bleaching clay is respectively as base
Plinth oil and tapped oil, improve base oil yield and extract oil yield out.4) for having for being contacted with spent bleaching clay
Machine solvent comes from the extraction solvent that solvent refining is carried out to solvent refining feedstock oil, forms whole system
The entirety of one organic circulation.
Under preferable case, isolated aqueous solutions of organic solvent backs into solvent recovery after the 3rd contact
System, respectively obtains the water of dry solvent and desolvation.Organic solvent and water can be recycled, not to ring
Border produces harm, and the water isolated is also preferably used for contacting with after-treatment spent bleaching clay, to dissolve spent bleaching clay
In organic solvent.Furthermore, refined liquid and Extract are subjected to water isolated after solvent recovery and may be used also
For being contacted with spent bleaching clay, to dissolve the organic solvent in spent bleaching clay.In addition, removing oil product is useless white
Soil can reduce influence of the oil-containing solids discarded object to environment after dehydration as cement producting material.
Other features and advantages of the present invention are described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with
Following embodiment is used to explain the present invention together, but is not construed as limiting the invention.
The flow chart of oil recovery method in the spent bleaching clay that Fig. 1 provides for the present invention.
Description of reference numerals
1- raw material oil pipelines；2- oil-containing solutions pipelines；3- solvent columns；4- oil-solvent mixture pipeline
5- extraction solvent pipelines；6- refined liquid pipelines；7- Extract pipelines；8- solvent recovering systems；
9- refines oil pipeline；10- extracts oil pipeline out；11- solvent dewaxing systems；12- dewaxing oil pipelines；
13- gatch pipelines；The clay-filtered systems of 14-；15- spent bleaching clay pipelines；16- bases oil pipeline；
17- spent bleaching clay oil recovery apparatus；18- organic solvent pipelines；19- solvent separate pipelines；
20- reuse pipelines；The return lines of 21- first；The return lines of 22- second；
23- de-oiling spent bleaching clay pipelines.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
According to the present invention, spent bleaching clay contains lube base described in oily recovery method in the spent bleaching clay
Oil and undesirable components, wherein, the recovery method includes：
Under the first contact conditions, by pending spent bleaching clay and organic solvent exposure, to be desorbed in spent bleaching clay
Lube base oil, and separation of solid and liquid obtains the mixture containing lube base oil and organic solvent
And spent bleaching clay is handled for the first time；
Under the second contact conditions, the spent bleaching clay handled for the first time and organic solvent exposure are given up in vain with dissolving
Undesirable components in soil, and separation of solid and liquid, obtain oil-containing solutions and after-treatment spent bleaching clay；
Under the 3rd contact conditions, after-treatment spent bleaching clay is contacted with water, to dissolve having in spent bleaching clay
Machine solvent, and separation of solid and liquid, obtain aqueous solutions of organic solvent and de-oiling spent bleaching clay；
Organic solvent used comes from molten to the progress of solvent refining feedstock oil in first contact and the second contact
The refined extraction solvent of agent；Wherein, the organic solvent can arise directly from outside and be carried for solvent refining
The fresh extraction solvent that supplies or gained refined liquid, raffinate after solvent refining are passed through into solvent
The extraction solvent of separated obtained recovery after recovery.
The isolated mixture containing lube base oil and organic solvent is returned, as to molten
Agent refined material oil carries out a part for the extraction solvent of solvent refining, and lube base oil is contained in the part
Extracting of the extraction solvent that can be provided with the mixture of organic solvent with outside together as solvent refining
Solvent.
The isolated oil-containing solutions are returned, and are used as a part for solvent refining feedstock oil, the part
Oil-containing solutions enter solvent refining system together with the feedstock oil that outside is provided and carry out solvent refining.
Wherein, the undesirable components in the spent bleaching clay mainly include colloid, polycyclic aromatic hydrocarbon, hetero atom
The many kinds of substance such as compound (sulfide, nitride and oxide), trace solvent, moisture and mechanical admixture,
Because raw material is different with technique, the species and content of undesirable components also can slightly difference, but do not influence this
Invent the effect of the recovery method.
In the present invention, the spent bleaching clay is that carclazyte refined material oil is carried out at clay finishing process
Discarded object after reason, the undesirable components during the post-refining in bleaching earth adsorption oil.The carclazyte
Refined material oil refers to the dewaxed oil after solvent refining and solvent dewaxing processing, and specifically, the present invention is right
The species of the clay-filtered feedstock oil is not particularly limited, and can be more than for existing various boiling points
300 DEG C and the dewaxed oil after solvent refining-solvent dewaxing processing, for example, can be vacuum distillate warp
Dewaxed oil that solvent refining-solvent dewaxing is obtained, solvent-deasphalted oils are obtained through solvent refining-solvent dewaxing
At least one of dewaxed oil.Wherein, the vacuum distillate can be Light lube oil, subtract three
Line distillate, the line distillate that subtracts four, at least one of the line distillate etc. that subtracts five.
The present invention dissolves spent bleaching clay by the base oil in organic solvent rinsing desorption spent bleaching clay, organic solvent
The method of organic solvent in the undesirable components such as middle colloid and heteroatomic compound and water dissolving spent bleaching clay
Oil product in spent bleaching clay is reclaimed, and the mixture containing most of base oil-organic solvent is returned
Solvent refining is returned as extraction solvent, ensure that base oil therein again passes by solvent refining, solvent
Dewaxing and clay finishing, again as lube base oil product, reduce what is adhered in spent bleaching clay
The loss of lube base oil, improves clay-filtered oil yield.Colloid and heteroatomic compound will be contained
The return solvent refining of the organic solvent containing undesirable components Deng impurity is fed as feedstock oil, non-ideal group
Lease making is crossed solvent refining and entered in tapped oil, improves the yield of solvent refining byproduct.In addition, being used for
It is molten that the organic solvent contacted with spent bleaching clay comes from the extracting for carrying out solvent refining to solvent refining feedstock oil
Agent, so that whole system forms the entirety of an organic circulation, is realized oily effective in carclazyte
Reclaim, and without individually building separation, retracting device, improve organic efficiency, greatly reduce simultaneously
Cost.
According to the present invention, the condition of first contact, the second contact and the 3rd contact includes contact
Temperature and the time of contact.
Specifically, the condition of first contact includes：Contact Temperature is 40-60 DEG C, is preferably
45-55℃.Organic solvent is contacted with spent bleaching clay at the temperature disclosed above and ensure that what is adhered in spent bleaching clay
Lube base oil is fully washed down so that lube base oil realizes physical separation with spent bleaching clay,
As long as the time of contact ensures as far as possible fully to be desorbed lube base oil i.e. from spent bleaching clay
Can, for example, time of contact is 5-20 minutes, preferably 10-15 minutes.
Furtherly, in order to reach that more preferably separating effect ensures the efficient utilization of organic solvent again, preferably
In the case of, under the first contact conditions, the mass ratio of organic solvent and pending spent bleaching clay is 3.5-6:1,
More preferably 4-5.5:1.
Specifically, second contact conditions include：Contact Temperature is 70-150 DEG C, is preferably
80-110℃.Organic solvent is contacted with first processing spent bleaching clay at the temperature disclosed above and ensure that spent bleaching clay
In undesirable components be completely dissolved in organic solvent, and separated from spent bleaching clay, time of contact is only
Ensure that fully dissolution is i.e. from spent bleaching clay by undesirable components such as colloid and heterocyclic compounds as far as possible
Can, for example, time of contact is 15-35 minutes, preferably 20-30 minutes.
Furtherly, in order to reach that more preferably separating effect ensures the efficient utilization of organic solvent again, preferably
In the case of, under the second contact conditions, the mass ratio of organic solvent and pending spent bleaching clay is 1.5-3.5:1,
Preferably 2-3:1.
Specifically, the 3rd contact conditions include：Contact Temperature is 80-95 DEG C, is preferably
85-90℃.Water is contacted with after-treatment spent bleaching clay at the temperature disclosed above and ensure that and fill organic solvent
Divide dissolution, and separated from spent bleaching clay, as long as the time of contact ensures as fully that organic solvent is molten as possible
In Xie Yushui and separate.
Furtherly, in order to reach that more preferably separating effect ensures under the efficient utilization of water, preferable case again,
Under the 3rd contact conditions, the mass ratio of water and pending spent bleaching clay is 1.5-3:1, preferably 1.8-2.5:1.
According to the present invention, the way of contact of organic solvent and spent bleaching clay and the way of contact of water and spent bleaching clay
Can be mixing, the mode of the mixing be able to can also be adopted using the mixing of auger conveyor circulation stirring
Stirred and mixed with agitating paddle, solid-liquid mixing belongs to routine techniques, will not be repeated here.
According to the present invention, the separation of solid and liquid after the first contact can be using the conventional separation of solid and liquid side in this area
Formula, organic solvent for example, natural subsidence is separated, specifically, first contacted with spent bleaching clay and (stir mixed
Close) after, stop stirring, keep temperature during contact (mixing) to be settled, isolate upper strata
Clear liquid is used as oil-solvent mixture.Specifically, settling temperature be 40-60 DEG C, preferably 45-55 DEG C,
It is more preferably identical with the Contact Temperature in the first contact conditions.As long as the sedimentation time guarantees to be layered and filled
Separation, for example, the sedimentation time is 100-180 minutes, preferably 115-155 minutes.
Furtherly, in order to which the supernatant liquor obtained after the first contact and separation of solid and liquid does not contain spent bleaching clay
Particle, preferably also includes being filtered supernatant liquor, and filter residue can together be carried out with first processing spent bleaching clay
Next step processing.Wherein, the method for the filtering can use prior art, will not be repeated here.
According to the present invention, the separation of solid and liquid after the second contact is preferred to use the method being separated by filtration, will be organic
Solvent is contacted after (stirring is mixed) with first processing spent bleaching clay, stops stirring, and keeping contact, (mixing is stirred
Mix) when temperature filtered, to obtain not containing the oil-containing solutions of spent bleaching clay particle after being contacted second,
The after-treatment spent bleaching clay filter cake for isolating oil-containing solutions keeps constant.Specifically, filtration temperature is
It is 70-150 DEG C, preferably 80-110 DEG C, more preferably identical with the Contact Temperature in the second contact conditions.Institute
It can be at least one of press filtration and suction filtration to state filtering, and the method for press filtration and suction filtration can use this area
Known prior art, will not be repeated here.
According to the present invention, under preferable case, the 3rd contact reclaimed water connects with spent bleaching clay in after-treatment filter cake
The mode of touching uses suction filtration and/or press filtration using the separation of solid and liquid after the method for diafiltration and contact, preferably takes out
The method of filter, wherein, the method for the diafiltration is included under vacuum or pressure effect, preferably makees in vacuum
Under, with Water spray after-treatment spent bleaching clay filter cake surface and filter cake is penetrated through, water is from another table of filter cake
Surface current goes out, and the organic solvent in spent bleaching clay is dissolved when oozing filter cake, obtains aqueous solutions of organic solvent and de-
Oily spent bleaching clay.With the increase of amount of seepage or time, the content of organic solvent is gradually reduced in filter cake,
And the content for permeating organic solvent in water is also reduced.Therefore, infiltration is than (water and the mass ratio of spent bleaching clay)
Size determine time of penetration, that is to say, that infiltration is than bigger, and the time of contact of water and carclazyte is longer.
After contact (diafiltration) terminates, that is, after the feeding for stopping water, by suction filtration and/or press filtration, preferably take out
Filter so that the water in spent bleaching clay is separated under pressure (malleation or negative pressure) effect with spent bleaching clay filter cake.Tool
For body, the temperature of separation of solid and liquid can be 80-95 DEG C, preferably 85-90 DEG C, more preferably be connect with the 3rd
Contact Temperature in touch article part is identical, and relative vacuum pressures can be -100kPa to -60kPa.
According to the present invention, water used comes from the fresh water of outside introducing in the 3rd contact.Under preferable case,
In order to effectively improve the utilization rate of water, in the 3rd contact, water used comes from is carried out to solvent refining feedstock oil
Water isolated after solvent recovery is carried out to gained refined liquid and raffinate after solvent refining.Meanwhile, the
Isolated aqueous solutions of organic solvent is preferably returned to solvent recovering system after three contacts, respectively obtains dry molten
Agent is (aqueous<0.5 mass %) and desolvation water so that organic solvent and water can circulate again sharp respectively
With therefore, water used can also come from water isolated after the solvent recovery in the 3rd contact.
According to the present invention, under preferable case, the organic solvent is that the extracting that solvent refining unit is used is molten
Agent, the one or more in furfural, 1-METHYLPYRROLIDONE and phenol, more preferably with solvent essence
Extraction solvent used in system is identical.
Oily recovery method can be operated continuously in the spent bleaching clay that the present invention is provided, can also intermittently operated.
Present invention also offers a kind of preparation method of lube base oil, wherein, the preparation method bag
Include：Feedstock oil is contacted into progress solvent refining with extraction solvent, refined liquid and Extract is obtained, carries out molten
Agent is reclaimed and respectively obtains refined oil, tapped oil, recycling design and water, by refined oil and dewaxing retarder thinner
Contact carries out solvent dewaxing, obtains dewaxed oil and gatch, and dewaxed oil is contacted into progress carclazyte benefit with carclazyte
Fill refined, obtain lube base oil and spent bleaching clay, the spent bleaching clay contains lube base oil and unreasonably
Think component, the preparation method also includes：
Under the first contact conditions, by pending spent bleaching clay and organic solvent exposure, to be desorbed in spent bleaching clay
Lube base oil, and separation of solid and liquid obtains the mixture containing lube base oil and organic solvent
And spent bleaching clay is handled for the first time；
Under the second contact conditions, spent bleaching clay and organic solvent exposure will be handled for the first time, to dissolve spent bleaching clay
In undesirable components, and separation of solid and liquid obtains oil-containing solutions and after-treatment spent bleaching clay；
Under the 3rd contact conditions, after-treatment spent bleaching clay is contacted with water, to dissolve having in spent bleaching clay
Machine solvent, and separation of solid and liquid, obtain aqueous solutions of organic solvent and de-oiling spent bleaching clay；
Organic solvent used comes from molten to the progress of solvent refining feedstock oil in first contact and the second contact
The refined extraction solvent of agent；
The isolated mixture containing lube base oil and organic solvent is returned, as to molten
Agent refined material oil carries out a part for the extraction solvent of solvent refining；
The isolated oil-containing solutions are returned, and are used as a part for solvent refining feedstock oil.
In addition to the method that recovery oily in the spent bleaching clay is provided according to the present invention is implemented, oil base is lubricated
Other steps in the preparation method of plinth oil, for example：Solvent refining, solvent recovery, solvent recycle,
The step of solvent dewaxing and clay finishing, may be referred to the process conditions and method of prior art,
And can summarize as the description below.
In simple terms, extraction solvent used is usually organic solvent in the solvent refining step, described to have
The conventional solvent that machine solvent can be known to the skilled person.It is described organic molten under preferable case
One or more of the agent in furfural, phenol, dimethyl sulfoxide (DMSO) and 1-METHYLPYRROLIDONE.
Solvent refining feedstock oil is contacted into progress solvent refining with extraction solvent generally to carry out in extraction tower.
This method includes：By feedstock oil and extraction solvent in extraction tower counter current contacting, obtained by extracting column overhead
Refined liquid, sends refined liquid into solvent recovering system, is separated by solvent, and essence is isolated from refined liquid
Liquefaction and extraction solvent, obtain Extract from extraction tower bottom of towe, Extract are sent into solvent recovering system,
Separated by solvent, tapped oil and extraction solvent are isolated from Extract.The extracting column overhead temperature
Spend for 60 DEG C to 140 DEG C, preferably 80 DEG C to 135 DEG C, the extraction tower column bottom temperature be 45 DEG C extremely
95 DEG C, preferably 60 DEG C to 90 DEG C.The extraction solvent and the oily mass ratio of refined material can be
0.5-5:1, preferably 1.5-4.5:1.
In simple terms, refined liquid and Extract are subjected to solvent recovery respectively, isolated refined oil, taken out
Fuel-displaced, recycling design and water, and the refined oil isolated is sent into solvent dewaxing.Generally, solvent recovery
Recovery including organic solvent in the recovery of organic solvent, Extract in refined liquid, the organic solvent reclaimed
Water removal dry and water the part of recovery four, therefore, can be obtained after solvent recovery refined oil,
Tapped oil, the dried organic solvent reclaimed are (aqueous<0.5 mass %) and reclaim water, the present invention
The organic solvent after drying water removal that described recycling design also refers to reclaim is (aqueous<0.5 mass %).
In simple terms, the solvent dewaxing refers to that (it is refined that solvent refining is obtained by solvent dewaxing feedstock oil
Oil) with dewaxing retarder thinner mixture dewaxed under dewaxing conditions.The dewaxing refers to：By original
The mixture of material oil and the retarder thinner that dewaxes is refrigerated to low temperature (dewaxing temperatures of Dewaxing conditions) and filtered,
The component separated out under low temperature from dewaxing fluid is (higher containing the slightly higher sweat oil component of condensation point and condensation point
Wax component) separation, obtain the process of dewaxed filtrate and slack wax.
Under normal circumstances, the dewaxing retarder thinner contains the fragrance of C3-C6 aliphatic ketone and C6-C8
Hydrocarbon.The aliphatic ketone of C3-C6 in the dewaxing retarder thinner is preferably acetone and/or butanone, described
C6-C8 aromatic hydrocarbon is preferably benzene and/or toluene.With C3-C6 aliphatic ketone and C6-C8 aromatic hydrocarbon
Cumulative volume on the basis of, C3-C6 alkenolic volume content is preferably 40% to 80%, C6-C8's
The volume content of aromatic hydrocarbon is preferably 20% to 60%, further preferably, with C3-C6 aliphatic ketone and
On the basis of the cumulative volume of C6-C8 aromatic hydrocarbon, C3-C6 alkenolic volume content is 45% to 75%,
The volume content of C6-C8 aromatic hydrocarbon is 25% to 55%.The dewaxing retarder thinner and dewaxed basestock oils
Mass ratio can be 1-7:1, preferably 2.0-5.5:1.
In simple terms, the clay finishing refers to that (solvent dewaxing is obtained by clay-filtered feedstock oil
Dewaxed oil) refined with the mixture of carclazyte under purification condition.Described refine refers to：Carclazyte is pressed
It is added to according to certain proportion in clay-filtered feedstock oil, clay-filtered feedstock oil is heated to carclazyte mixture
The extraction temperature of purification condition, contacts and filters by the stirring of certain time, the oil product (base after refining
Plinth oil) separated with spent bleaching clay, obtain the process of base oil and spent bleaching clay.
The carclazyte is the high-quality bentonite that montmorillonite is more than 85%, it is preferably activated after carclazyte.With
On the basis of the gross mass of clay-filtered feedstock oil, the addition of carclazyte can be 1-12 mass %, be preferably
3-7 mass %.Contact Temperature can be 100-280 DEG C, preferably 120-260 DEG C.Time of contact can be with
For 20-60min, preferably 25-50min.
Oily recovery method carries out further detailed in the spent bleaching clay provided below by 1 couple of present invention of accompanying drawing
Thin description.
As shown in figure 1, feedstock oil introduces solvent column through raw material oil pipeline 1 and oil-containing solutions pipeline 2
3 bottoms, with introducing the top of solvent column 3 through extraction solvent pipeline 5, oil-solvent mixture pipeline 4
Solvent counter current contact, obtain refined liquid and Extract.Extract flows out from the bottom of towe of solvent column 3,
Desolvation in solvent recovering system 8 is introduced into through Extract pipeline 7, is taken out through extracting oil pipeline 10 out
It is fuel-displaced.Refined liquid is flowed out from the tower top of solvent column 3, and solvent recovering system is introduced through refined liquid pipeline 6
8 desolvations, obtain lube base oil refined oil.Lube base oil refined oil is through refined oil pipeline
9, which introduce the middle high condensation point component of raffinating oil of removing under solvent dewaxing systems 11, low temperature, obtains dewaxed oil, through containing
Oily ceratuba line 13 obtains gatch.Dewaxed oil introduces clay-filtered system 14 through the oil pipeline 12 that dewaxes, and inhales
Undesirable components in attached dewaxed oil, obtain lube base oil, spent bleaching clay is through useless through basic oil pipeline 16
Carclazyte pipeline 15 enter in spent bleaching clay oil recovery apparatus 17 with through organic solvent pipeline 18 introduce it is organic
(organic solvent comes from the extraction solvent for entering solvent column 3, further for solvent contact
The refined liquid after solvent refining and Extract are preferably subjected to recovery isolated after solvent recovery molten
Agent)；The spent bleaching clay oil recovery apparatus 17 generally includes mixing arrangement and filter, wherein first connects
Sedimentation after tactile and the first contact, and the second contact and the 3rd contact can be directly in mixing arrangements
Carry out, suction filtration can be in filtering dress after the filtering and the 3rd contact (diafiltration) and contact after the second contact
Put middle progress, in addition, operate for convenience, the spent bleaching clay oil recovery apparatus 17 can also be it is multiple,
First contact, the second contact and the 3rd contact are entered in each independent spent bleaching clay oil recovery apparatus respectively
Row operation), mixture is after sedimentation separation, and upper strata oil-solvent mixture enters through the first return line 21
Enter the solvent line of solvent column 3, enter solvent column 3 through oil-solvent mixture pipeline 4.Under
The first processing spent bleaching clay of layer continues the organic solvent exposure with being introduced through organic solvent pipeline 18, passes through
After filter separation, oil-containing solutions enter the raw material oil pipeline of solvent column 3 through the second return line 22,
Enter solvent column 3 through oil-containing solutions pipeline 2.The after-treatment spent bleaching clay of lower floor with through reuse pipeline
(water comes preferably from carries out solvent time to 20 water introduced by the refined liquid after solvent refining and Extract
After receipts isolated water and/or will above-mentioned aqueous solutions of organic solvent carry out solvent recovery after it is isolated
Water) contacted by being percolated mode after, aqueous solutions of organic solvent enters solvent through solvent separate pipeline 19 and returned
Receipts system 8, three times processing spent bleaching clay be dehydrated through suction filtration after by the discharger of de-oiling spent bleaching clay pipeline 23.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited to above-mentioned reality
The detail in mode is applied, can be to technical side of the invention in the range of the technology design of the present invention
Case carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention no longer separately illustrates to various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
The present invention will be described in detail by way of examples below.
Comparative example 1
Using solvent refining-solvent dewaxing-clay finishing flow production lube base oil, to subtract two
Line distillate is used as solvent refining feedstock oil.
In solvent refining step：Extraction solvent is furfural.The matter of extraction solvent and solvent refining feedstock oil
Amount is than being 1.5:1, extracting column overhead and column bottom temperature are respectively 80 DEG C and 60 DEG C.From the tower top of extraction tower
Refined oil is isolated in refined liquid, tapped oil is isolated from extraction tower bottom of towe Extract.
In solvent dewaxing step：In the mixture that retarder thinner is butanone and toluene used that dewaxes, mixture
Butanone volume content is 75%, and volume of toluene content is 25%.Refined oil feedstock oil fusion temperature is 70 DEG C,
The mass ratio of dewaxing retarder thinner and refined oil feedstock oil is 2:1, by the refined oil feedstock oil of fusing with taking off
Wax retarder thinner is mixed, frozen cooling, and dewaxing filtration temperature is -22 DEG C, and dewaxed filtrate is obtained after filtering
With oil-containing slack wax, dewaxed oil is obtained after dewaxed filtrate is removed into solvent.
Clay finishing is carried out by feedstock oil of the solvent refining dewaxed oil of Light lube oil, carclazyte is mended
Fill in purification step：On the basis of the gross mass of clay-filtered feedstock oil, carclazyte addition is 3% (weight
Amount), Contact Temperature is 120 DEG C, and time of contact is carclazyte oily based on obtaining after 40min, filtering
Refined oil and spent bleaching clay.
Base oil comprehensive yield and property are shown in Table 1.
Base oil comprehensive yield calculation formula is：
Base oil comprehensive yield=(solvent refining oil yield/100) × (yield dewaxed oil/100) × (white
Native oil yield/100) × 100.
Base oil comprehensive yield calculation formula is identical in following comparative example.
Embodiment 1
The embodiment is used to illustrate recovery method oily in the spent bleaching clay of the invention provided.
Lube base oil is produced using with the identical raw material of comparative example 1, technological process and condition, it is different
, the spent bleaching clay obtained to clay finishing according to Fig. 1 flow carries out recovery oily in spent bleaching clay.
Experiment for the first time is using the clay-filtered spent bleaching clay obtained in comparative example 1, and second experiment uses the
Obtained spent bleaching clay is once tested, repeats to test repeatedly, when double experimental result is identical, takes most
The result once tested afterwards, is specifically shown in Table 2.
Base oil comprehensive yield calculation formula is in table：
Base oil comprehensive yield=(solvent refining oil yield/100) × (yield dewaxed oil/100) × (white
Native oil yield/100) × 100.
Base oil comprehensive yield increment rate calculation formula is in table：
Base oil comprehensive yield increment rate=100 × [base oil comprehensive yield (using the inventive method)-base
Plinth oil comprehensive yield (using conventional method)]/base oil comprehensive yield (using the inventive method)
Base oil comprehensive yield and base oil comprehensive yield increment rate calculation formula are identical in following examples.
Comprise the following steps that：Addition organic solvent furfural in step a, spent bleaching clay, furfural and spent bleaching clay
Mass ratio is 4:1, it is 50 DEG C to mix temperature, and the mixing time is 10min, and mixture is at 50 DEG C
Under the conditions of settle 115min, separate fuel-displaced-solvent mixture, obtain handling spent bleaching clay for the first time.Step b,
The mass ratio of addition organic solvent furfural in first processing spent bleaching clay, furfural and spent bleaching clay is 2:1, mixing
Whipping temp is 93 DEG C, and the mixing time is 25min, and filtration temperature is 93 DEG C, mixture filtering
Isolated oil-containing solutions and after-treatment spent bleaching clay.Step c, coolant-temperature gage is 85 DEG C, using diafiltration
Mode rinses after-treatment spent bleaching clay filter cake with water and carries out separation of solid and liquid using suction filtration, water and spent bleaching clay
Mass ratio is 2:1, obtain containing aqueous solvent and de-oiling spent bleaching clay.
Oil-solvent mixture enters the solvent line of solvent column, and oil-containing solutions enter solvent column
Raw material oil pipeline, enter solvent recovering system containing aqueous solvent, the de-oiling spent bleaching clay after dehydration goes out device.
Comparative example 2
Using solvent refining-solvent dewaxing-clay finishing flow production lube base oil, to subtract three
Line distillate is used as solvent refining feedstock oil.
In solvent refining step：Extraction solvent is furfural.The matter of extraction solvent and solvent refining feedstock oil
Amount is than being 2.5:1, extracting column overhead and column bottom temperature are respectively 110 DEG C and 70 DEG C.From the tower top of extraction tower
Refined oil is isolated in refined liquid, tapped oil is isolated from extraction tower bottom of towe Extract.
In solvent dewaxing step：In the mixture that retarder thinner is butanone and toluene used that dewaxes, mixture
Butanone volume content is 60%, and volume of toluene content is 40%.Refined oil feedstock oil fusion temperature is 70 DEG C,
The mass ratio of dewaxing retarder thinner and refined oil feedstock oil is 3.5:1, by the refined oil feedstock oil of fusing with taking off
Wax retarder thinner is mixed, frozen cooling, and dewaxing filtration temperature is -25 DEG C, and dewaxed filtrate is obtained after filtering
With oil-containing slack wax, dewaxed oil is obtained after dewaxed filtrate is removed into solvent.
Clay finishing, carclazyte essence are carried out by feedstock oil of the solvent refining dewaxed oil for the line distillate that subtracts three
In step processed, on the basis of the gross mass of clay-filtered feedstock oil, carclazyte addition is 4% (weight),
Contact Temperature is 160 DEG C, and time of contact is oily clay-filtered based on obtaining after 50min, filtering
Oil and spent bleaching clay.
Base oil comprehensive yield and property are shown in Table 1.
Embodiment 2
The embodiment is used to illustrate recovery method oily in the spent bleaching clay of the invention provided.
Lube base oil is produced using with the identical raw material of comparative example 2, technological process and condition, it is different
, the spent bleaching clay obtained to clay finishing according to Fig. 1 flow carries out recovery oily in spent bleaching clay.
Experiment for the first time is using the clay-filtered spent bleaching clay obtained in comparative example 2, and second of experiment is used for the first time
Obtained spent bleaching clay is tested, repeats to test repeatedly, when double experimental result is identical, takes last
The result of secondary experiment, is specifically shown in Table 2.
Comprise the following steps that：Addition organic solvent furfural in step a, spent bleaching clay, furfural and spent bleaching clay
Mass ratio is 4.3:1, it is 45 DEG C to mix temperature, and the mixing time is 15min, and mixture exists
125min is settled under the conditions of 45 DEG C, fuel-displaced-solvent mixture is separated, obtains handling spent bleaching clay for the first time.Step
The mass ratio of addition organic solvent furfural in rapid b, first processing spent bleaching clay, furfural and spent bleaching clay is 2.2:1,
It is 80 DEG C to mix temperature, and the mixing time is 30min, and filtration temperature is 80 DEG C, mixture
It is separated by filtration and obtains oil-containing solutions and after-treatment spent bleaching clay.Step c, coolant-temperature gage is 90 DEG C, using oozing
The mode of filter rinses after-treatment spent bleaching clay filter cake with water and carries out separation of solid and liquid using suction filtration, and water is white with giving up
The mass ratio of soil is 2.3:1, obtain containing aqueous solvent and de-oiling spent bleaching clay.
Oil-solvent mixture enters the solvent line of solvent column, and oil-containing solutions enter solvent column
Raw material oil pipeline, enter solvent recovering system containing aqueous solvent, the de-oiling spent bleaching clay after dehydration goes out device.
Comparative example 3
Using solvent refining-solvent dewaxing-clay finishing flow production lube base oil, to subtract four
Line distillate is used as solvent refining feedstock oil.
In solvent refining step：Extraction solvent is furfural.The matter of extraction solvent and solvent refining feedstock oil
Amount is than being 3.5:1, extracting column overhead and column bottom temperature are respectively 120 DEG C and 75 DEG C.From the tower top of extraction tower
Refined oil is isolated in refined liquid, tapped oil is isolated from extraction tower bottom of towe Extract.
In solvent dewaxing step：In the mixture that retarder thinner is butanone and toluene used that dewaxes, mixture
Butanone volume content is 55%, and volume of toluene content is 45%.Refined oil feedstock oil fusion temperature is 70 DEG C,
The mass ratio of dewaxing retarder thinner and refined oil feedstock oil is 4:1, by the refined oil feedstock oil of fusing with taking off
Wax retarder thinner is mixed, frozen cooling, and dewaxing filtration temperature is -22 DEG C, and dewaxed filtrate is obtained after filtering
With oil-containing slack wax, dewaxed oil is obtained after dewaxed filtrate is removed into solvent.
Clay finishing is carried out by feedstock oil of the solvent refining dewaxed oil for the line distillate that subtracts four, carclazyte is mended
Fill in purification step：On the basis of the gross mass of clay-filtered feedstock oil, carclazyte addition is 5% (weight
Amount), Contact Temperature is 200 DEG C, and time of contact is carclazyte oily based on obtaining after 25min, filtering
Refined oil and spent bleaching clay.
Base oil comprehensive yield and property are shown in Table 1.
Embodiment 3
The embodiment is used to illustrate recovery method oily in the spent bleaching clay of the invention provided.
Lube base oil is produced using with the identical raw material of comparative example 3, technological process and condition, it is different
, the spent bleaching clay obtained to clay finishing according to Fig. 1 flow carries out recovery oily in spent bleaching clay.
Experiment for the first time is using the clay-filtered spent bleaching clay obtained in comparative example 3, and second of experiment is used for the first time
Obtained spent bleaching clay is tested, repeats to test repeatedly, when double experimental result is identical, takes last
The result of secondary experiment, is specifically shown in Table 2.
Comprise the following steps that：Addition organic solvent furfural in step a, spent bleaching clay, furfural and spent bleaching clay
Mass ratio is 4.5:1, it is 55 DEG C to mix temperature, and the mixing time is 12min, and mixture exists
140min is settled under the conditions of 55 DEG C, fuel-displaced-solvent mixture is separated, obtains handling spent bleaching clay for the first time.Step
The mass ratio of addition organic solvent furfural in rapid b, first processing spent bleaching clay, furfural and spent bleaching clay is 2.5:1,
It is 97 DEG C to mix temperature, and the mixing time is 20min, and filtration temperature is 97 DEG C, mixture
It is separated by filtration and obtains oil-containing solutions and after-treatment spent bleaching clay.Step c, coolant-temperature gage is 90 DEG C, using oozing
The mode of filter rinses after-treatment spent bleaching clay filter cake with water and carries out separation of solid and liquid using suction filtration, and water is white with giving up
The mass ratio of soil is 1.8:1, obtain containing aqueous solvent and de-oiling spent bleaching clay.
Oil-solvent mixture enters the solvent line of solvent column, and oil-containing solutions enter solvent column
Raw material oil pipeline, enter solvent recovering system containing aqueous solvent, the de-oiling spent bleaching clay after dehydration goes out device.
Comparative example 4
Using solvent refining-solvent dewaxing-clay finishing flow production lube base oil, with frivolous
Oil is used as solvent refining feedstock oil.
In solvent refining step：Extraction solvent is furfural.The matter of extraction solvent and solvent refining feedstock oil
Amount is than being 4.5:1, extracting column overhead and column bottom temperature are respectively 135 DEG C and 90 DEG C.From the tower top of extraction tower
Refined oil is isolated in refined liquid, tapped oil is isolated from extraction tower bottom of towe Extract.
In solvent dewaxing step：In the mixture that retarder thinner is butanone and toluene used that dewaxes, mixture
Butanone volume content is 45%, and volume of toluene content is 55%.Refined oil feedstock oil fusion temperature is 70 DEG C,
The mass ratio of dewaxing solvent and refined oil feedstock oil is 5.5:1, the refined oil feedstock oil of fusing is dilute with dewaxing
Solvent mixing is released, frozen cooling, dewaxing filtration temperature is -20 DEG C, and dewaxed filtrate is obtained after filtering and is contained
Oily slack wax, dewaxed oil is obtained after dewaxed filtrate is removed into solvent.
Clay finishing, clay-filtered step are carried out by feedstock oil of frivolous oily solvent refining dewaxed oil
In, on the basis of the gross mass of clay-filtered feedstock oil, carclazyte addition is 7% (weight), contact temperature
Spend for 260 DEG C, time of contact is clay-filtered oil oily based on obtaining after 35min, filtering and useless
Carclazyte.
Base oil comprehensive yield and property are shown in Table 1.
Embodiment 4
The embodiment is used to illustrate recovery method oily in the spent bleaching clay of the invention provided.
Lube base oil is produced using with the identical raw material of comparative example 4, technological process and condition, it is different
, the spent bleaching clay obtained to clay finishing according to Fig. 1 flow carries out recovery oily in spent bleaching clay.
Experiment for the first time is using the clay-filtered spent bleaching clay obtained in comparative example 4, and second of experiment is used for the first time
Obtained spent bleaching clay is tested, repeats to test repeatedly, when double experimental result is identical, takes last
The result of secondary experiment, is specifically shown in Table 2.
Comprise the following steps that：Addition organic solvent furfural in step a, spent bleaching clay, furfural and spent bleaching clay
Mass ratio is 5.5:1, it is 55 DEG C to mix temperature, and the mixing time is 14min, and mixture exists
155min is settled under the conditions of 55 DEG C, fuel-displaced-solvent mixture is separated, obtains handling spent bleaching clay for the first time.Step
The mass ratio of addition organic solvent furfural in rapid b, first processing spent bleaching clay, furfural and spent bleaching clay is 3:1,
It is 110 DEG C to mix temperature, and the mixing time is 30min, and filtration temperature is 110 DEG C, mixture
It is separated by filtration and obtains oil-containing solutions and after-treatment spent bleaching clay.Step c, coolant-temperature gage is 89 DEG C, using oozing
The mode of filter rinses after-treatment spent bleaching clay filter cake with water and carries out separation of solid and liquid using suction filtration, and water is white with giving up
The mass ratio of soil is 2.5:1, obtain containing aqueous solvent and de-oiling spent bleaching clay.
Oil-solvent mixture enters the solvent line of solvent column, and oil-containing solutions enter solvent column
Raw material oil pipeline, enter solvent recovering system containing aqueous solvent, the de-oiling spent bleaching clay after dehydration goes out device.
Table 1
| Project | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Analysis method |
| Refined oil mass yield/% | 85.3 | 62.1 | 68.6 | 79.8 | - |
| Dewaxed oil mass yield/% | 55.6 | 83.4 | 79.5 | 48.2 | - |
| Carclazyte oil quality yield/% | 98.9 | 98.5 | 97.9 | 96.9 | - |
| Base oil comprehensive quality yield/% | 46.9 | 51.0 | 53.4 | 37.3 | - |
| Density (20 DEG C)/(kg/m3) | 883.5 | 882.8 | 884.8 | 906.1 | GB/T 13377 |
| Kinematic viscosity (40 DEG C)/(mm2/s) | 32.71 | 65.93 | 133.8 | / | GB/T 265 |
| Kinematic viscosity (100 DEG C)/(mm2/s) | / | / | / | 32.15 | GB/T 265 |
| Viscosity Index | 98 | 95 | 96 | 92 | - |
| Pour point/DEG C | -15 | -15 | -12 | -9 | GB/T 3535 |
| Color/number | 1 | 2 | 4 | 5.5 | GB/T 6540 |
| Oxidation stability/min | 237 | 219 | 193 | 182 | SH/T 0193 |
| Tapped oil mass yield/% | 14.7 | 37.9 | 31.4 | 20.2 | - |
Table 2
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Analysis method |
| Refined oil mass yield/% | 85.7 | 62.6 | 69.4 | 80.5 | - |
| Dewaxed oil mass yield/% | 55.8 | 83.5 | 79.7 | 48.7 | - |
| Carclazyte oil quality yield/% | 98.9 | 98.5 | 97.9 | 97.0 | - |
| Base oil comprehensive quality yield/% | 47.3 | 51.5 | 54.1 | 38.0 | - |
| Base oil comprehensive quality yield increment rate/% | 0.8 | 1.0 | 1.4 | 1.9 | - |
| Density (20 DEG C)/(kg/m3) | 883.3 | 882.9 | 884.6 | 906.5 | GB/T 13377 |
| Kinematic viscosity (40 DEG C)/(mm2/s) | 32.78 | 65.99 | 133.7 | / | GB/T 265 |
| Kinematic viscosity (100 DEG C)/(mm2/s) | / | / | / | 32.08 | GB/T 265 |
| Viscosity Index | 98 | 95 | 96 | 92 | - |
| Pour point/DEG C | -15 | -15 | -12 | -9 | GB/T 3535 |
| Color/number | 1 | 2 | 4 | 5.5 | GB/T 6540 |
| Oxidation stability/min | 235 | 221 | 194 | 183 | SH/T 0193 |
| Tapped oil mass yield/% | 14.9 | 38.2 | 31.8 | 20.7 | - |
The carclazyte supplement essence it can be seen from comparative example 1-4 and embodiment 1-4 clay finishing result
Spent bleaching clay processed through the present invention method carry out oil recycling after, identical raw material, technological process and
Under process conditions, the measured oil of matter is re-entered into lube base oil in spent bleaching clay, in base oil
While comprehensive yield is improved, basic oil quality does not change.Ropy oil is entered in tapped oil,
Tapped oil mass yield is improved.
Either with vacuum distillate still with solvent deasphalting it can be seen from embodiment 1-4 result
The solvent refining dewaxed oil of oil is raw material, and the oil in spent bleaching clay can be reclaimed using the method for the present invention
Point, compared with corresponding comparative example, lube base oil comprehensive quality yield increment rate is between 0.8-1.9%.
Using method of the invention, it is possible to reclaim the oil in spent bleaching clay, petroleum resources are taken full advantage of, are obtained
Solid waste without oil, reduces the pollution to environment, it is often more important that returned without newly-built solvent
Receipts system, so that equipment investment and the operating cost of solvent method processing spent bleaching clay is greatly reduced.
Claims (19)
1. a kind of oily recovery method in spent bleaching clay, the spent bleaching clay contains lube base oil and unreasonably
Think component, it is characterised in that the recovery method includes：
Under the first contact conditions, by pending spent bleaching clay and organic solvent exposure, to be desorbed in spent bleaching clay
Lube base oil, and separation of solid and liquid obtains the mixture containing lube base oil and organic solvent
And spent bleaching clay is handled for the first time；
Under the second contact conditions, spent bleaching clay and organic solvent exposure will be handled for the first time, to dissolve spent bleaching clay
In undesirable components, and separation of solid and liquid obtains oil-containing solutions and after-treatment spent bleaching clay；
Under the 3rd contact conditions, after-treatment spent bleaching clay is contacted with water, to dissolve having in spent bleaching clay
Machine solvent, and separation of solid and liquid, obtain aqueous solutions of organic solvent and de-oiling spent bleaching clay；
Organic solvent used comes from molten to the progress of solvent refining feedstock oil in first contact and the second contact
The refined extraction solvent of agent；
The isolated mixture containing lube base oil and organic solvent is returned, as to molten
Agent refined material oil carries out a part for the extraction solvent of solvent refining；
The isolated oil-containing solutions are returned, and are used as a part for solvent refining feedstock oil.
2. recovery method according to claim 1, wherein, first contact conditions include：
Contact Temperature is 40-60 DEG C, and preferably 45-55 DEG C, time of contact is 5-20 minutes, preferably 10-15
Minute；Under the first contact conditions, the mass ratio of organic solvent and pending spent bleaching clay is 3.5-6:1, it is excellent
Elect 4-5.5 as:1.
3. recovery method according to claim 1 or 2, wherein, by pending spent bleaching clay with having
The method of separation of solid and liquid after the contact of machine solvent is sedimentation, and settling temperature is 40-60 DEG C, is preferably
It is 45-55 DEG C, more preferably identical with the Contact Temperature in the first contact conditions.
4. recovery method according to claim 1, wherein, second contact conditions include：
Contact Temperature is 70-150 DEG C, and preferably 80-110 DEG C, time of contact is 15-35 minutes, preferably 20-30
Minute；Under the second contact conditions, the mass ratio of organic solvent and pending spent bleaching clay is 1.5-3.5:1,
Preferably 2-3:1.
5. the recovery method according to claim 1 or 4, wherein, will handle for the first time spent bleaching clay with
The method of separation of solid and liquid after organic solvent exposure is filtering, and filtration temperature is 70-150 DEG C, is preferably
It is 80-110 DEG C, more preferably identical with the Contact Temperature in the second contact conditions.
6. recovery method according to claim 1, wherein, the 3rd contact conditions include：
Contact Temperature is 80-95 DEG C, and preferably 85-90 DEG C, under the 3rd contact conditions, water gives up in vain with pending
The mass ratio of soil is 1.5-3:1, preferably 1.8-2.5:1.
7. the recovery method according to claim 1 or 6, wherein, by after-treatment spent bleaching clay with
The method of separation of solid and liquid is suction filtration after the method for water contact is diafiltration and contacted, the temperature of the separation of solid and liquid
Spend for 80-95 DEG C, preferably 85-90 DEG C, it is more preferably identical with the Contact Temperature in the 3rd contact conditions.
8. the recovery method according to claim 1 or 6, wherein, this method also includes will separation
Obtained aqueous solutions of organic solvent comes back for solvent recovery, isolated organic solvent and water, and the 3rd connects
Water used comes from water isolated after solvent recovery in touching.
9. the recovery method according to any one in claim 1-2,4 and 6, wherein, it is described
One or more of the organic solvent in furfural, 1-METHYLPYRROLIDONE and phenol, be preferably and solvent
Extraction solvent used in refined is identical.
10. recovery method according to claim 1, wherein, the spent bleaching clay is to clay-filtered
Feedstock oil carries out the discarded object after clay finishing process processing, and the clay-filtered feedstock oil is boiling point
More than 300 DEG C and the dewaxed oil after solvent refining-solvent dewaxing processing, be preferably selected from vacuum distillate and
At least one of dewaxed oil that solvent-deasphalted oils are obtained through solvent refining-solvent dewaxing, wherein, institute
It is Light lube oil, the line distillate that subtracts three, the line distillate that subtracts four and the line cut that subtracts five to state vacuum distillate
At least one of oil.
11. a kind of preparation method of lube base oil, it is characterised in that the preparation method includes：
Feedstock oil is contacted into progress solvent refining with extraction solvent, refined liquid and Extract is obtained, solvent is carried out and returns
Receipts respectively obtain refined oil, tapped oil, recycling design and water, and refined oil is contacted with dewaxing retarder thinner
Solvent dewaxing is carried out, dewaxed oil and gatch is obtained, dewaxed oil is contacted into progress carclazyte supplement essence with carclazyte
System, obtains lube base oil and spent bleaching clay, the spent bleaching clay contains lube base oil and non-ideal group
Point, the preparation method also includes：
Under the first contact conditions, by pending spent bleaching clay and organic solvent exposure, to be desorbed in spent bleaching clay
Lube base oil, and separation of solid and liquid obtains the mixture containing lube base oil and organic solvent
And spent bleaching clay is handled for the first time；
Under the second contact conditions, spent bleaching clay and organic solvent exposure will be handled for the first time, to dissolve spent bleaching clay
In undesirable components, and separation of solid and liquid obtains oil-containing solutions and after-treatment spent bleaching clay；
Under the 3rd contact conditions, after-treatment spent bleaching clay is contacted with water, to dissolve having in spent bleaching clay
Machine solvent, and separation of solid and liquid, obtain aqueous solutions of organic solvent and de-oiling spent bleaching clay；
Organic solvent used comes from molten to the progress of solvent refining feedstock oil in first contact and the second contact
The refined extraction solvent of agent；
The isolated mixture containing lube base oil and organic solvent is returned, as to molten
Agent refined material oil carries out a part for the extraction solvent of solvent refining；
The isolated oil-containing solutions are returned, and are used as a part for solvent refining feedstock oil.
12. preparation method according to claim 11, wherein, first contact conditions include：
Contact Temperature is 40-60 DEG C, and preferably 45-55 DEG C, time of contact is 5-20 minutes, preferably 10-15
Minute；Under the first contact conditions, the mass ratio of organic solvent and pending spent bleaching clay is 3.5-6:1, it is excellent
Elect 4-5.5 as:1.
13. the preparation method according to claim 11 or 12, wherein, by pending spent bleaching clay with
The method of separation of solid and liquid after organic solvent exposure is sedimentation, and settling temperature is 40-60 DEG C, is preferably
It is 45-55 DEG C, more preferably identical with the Contact Temperature in the first contact conditions.
14. preparation method according to claim 11, wherein, second contact conditions include：
Contact Temperature is 70-150 DEG C, and preferably 80-110 DEG C, time of contact is 15-35 minutes, preferably 20-30
Minute；Under the second contact conditions, the mass ratio of organic solvent and pending spent bleaching clay is 1.5-3.5:1,
Preferably 2-3:1.
15. the preparation method according to claim 11 or 14, wherein, spent bleaching clay will be handled for the first time
Method with the separation of solid and liquid after organic solvent exposure is filtering, and filtration temperature is 70-150 DEG C, is preferably
It is 80-110 DEG C, more preferably identical with the Contact Temperature in the second contact conditions.
16. preparation method according to claim 11, wherein, the 3rd contact conditions include：
Contact Temperature is 80-95 DEG C, and preferably 85-90 DEG C, under the 3rd contact conditions, water gives up in vain with pending
The mass ratio of soil is 1.5-3:1, preferably 1.8-2.5:1.
17. the preparation method according to claim 11 or 16, wherein, by after-treatment spent bleaching clay
The method of separation of solid and liquid is suction filtration after the method contacted with water is diafiltration and contacted, the separation of solid and liquid
Temperature is 80-95 DEG C, preferably 85-90 DEG C, more preferably identical with the Contact Temperature in the 3rd contact conditions.
18. the preparation method according to claim 11 or 16, wherein, this method also includes dividing
Solvent recovery, isolated organic solvent and water, the 3rd are come back for from obtained aqueous solutions of organic solvent
In contact water used come from by refined liquid and Extract carry out water isolated after solvent recovery and/or
It is above-mentioned that aqueous solutions of organic solvent is carried out to water isolated after solvent recovery.
19. the preparation method according to any one in claim 11-12,14 and 16, wherein,
One or more of the organic solvent in furfural, 1-METHYLPYRROLIDONE and phenol, be preferably with
Extraction solvent is identical used in solvent refining.
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| CN109722285A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | In spent bleaching clay in oily recovery method and spent bleaching clay oil recovery utilization method |
| CN109735391A (en) * | 2019-02-19 | 2019-05-10 | 安徽国孚凤凰科技有限公司 | A method of improving solvent refining reclaimed oil base oil yield |
| CN111073681A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Method for recovering oil from waste argil and method for preparing lubricating oil base oil |
| CN111908484A (en) * | 2020-07-10 | 2020-11-10 | 广东石油化工学院 | 4A molecular sieve and preparation method and application thereof |
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| CN109722285A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | In spent bleaching clay in oily recovery method and spent bleaching clay oil recovery utilization method |
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| CN111908484A (en) * | 2020-07-10 | 2020-11-10 | 广东石油化工学院 | 4A molecular sieve and preparation method and application thereof |
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