CN1143383A - Removing contaminants from oil - Google Patents
Removing contaminants from oil Download PDFInfo
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- CN1143383A CN1143383A CN95191643A CN95191643A CN1143383A CN 1143383 A CN1143383 A CN 1143383A CN 95191643 A CN95191643 A CN 95191643A CN 95191643 A CN95191643 A CN 95191643A CN 1143383 A CN1143383 A CN 1143383A
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- oil
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- pollutent
- oil plant
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- 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
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
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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
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Extraction Or Liquid Replacement (AREA)
- Physical Water Treatments (AREA)
Abstract
A process comprising combining the heavy oil still residue and propane in conduits (146) and pumping mixture through static mixer (300). The mixture is then passed through heat exchanger (301) and flows via (302) to an extraction vessel (304). The residum/oil mixture then leaves via outlet (308) and asphalt pump (309).
Description
Invention field
The present invention relates to crude oil or in the mineral oil of processing pollutant removing, relate to removing of pollutent in the useless motor oil particularly.The present invention relates to remove the method and apparatus of pollutent in the mineral oil.
Prior art
Known have a large amount of methods that removes pollutent in mineral oil and the waste lubricating oil in the prior art, and really, these too much prior art documents have illustrated that also people search out the unremitting effort that a kind of method that removes pollutent in the oil plant is at low cost done.
Undesirable pollutent generally includes the high molecular weight alkane complex mixture of (comprising naphthenic hydrocarbon) in the crude oil, i.e. pitch, and in oil vacuum distilling, pitch is recovered as the viscosity Residual oil, and knows that it can reduce the efficient of still-process.As everyone knows, removing in the prior art or reduce the bituminous method is with liquid solvent such as propane or butane crude oil to be carried out solvent extraction.
Useless motor oil contains various undesirable pollutents, " mixture " as carbon, some bituminous matter compounds and interpolation, it comprises organometallic compound, as rust-preventive agent, oxidation inhibitor, anti-wear agent, washing composition-dispersion agent and antifoams and synthetic polymeric pour point reducer and viscosity index improver.In useless motor oil, dissolved and undissolved metal value comprise calcium, phosphorus, sulphur, zinc, sodium and the magnesium of different amounts in lead (from gasoline), iron (from engine scuffing) and " mixture " that come from interpolation, except that organic compounds containing nitrogen.
Because organometallic compound and polymerizable compound are dissolved in the used solvent of solvent extraction removal process, and under the temperature similar, begin distillation, so be unusual difficulty by " mixture " that remove interpolation in the useless motor oil to the lubricant base oil.
Reclaim in the waste oil peculiar to vessel at the bottom of by cabin, water and stable oil/water miscible liquid are exactly pollutent, and are removed with being difficult for very economical.Therefore, waste oil peculiar to vessel can not be as the raw material of refinery, and this is owing to the danger that the refining action problem is arranged, and in treating processes relatively in a small amount, it is uneconomic that traditional propane extracts.
United States Patent (USP) NO.2196989 discloses a kind of by the method for separate asphaltenes compound in the crude oil with manufacturing lubricating oil.In the method, crude oil mixes with light varsol and rare gas element, varsol such as liquid propane gas or butane, and rare gas element such as methane, ethane, hydrogen, carbonic acid gas, nitrogen or ammonia, this gas is as the precipitation agent that is dissolved in the oily substance in the liquid solvent.
Under the temperature and pressure that raises, asphalt oil is contacted with the liquid solution of oil plant and propane, wherein, most oil plant is dissolved in the liquid propane gas liquation, the bottom that the undissolved pitch impurity of droplet is then fallen reaction vessel.Under elevated pressure, will be dissolved in liquid propane gas but the gas that is insoluble to mineral oil is being introduced in oil plant/propane liquor near the container top place.The precipitation agent gas dissolving and with its dilution, has reduced the solubleness of residual asphalt impurity thus in propane solution, finally be settled out pitch and most oil plant from solution.
By being settled out oiliness impurity by precipitation agent gas in the propane solution, it is said principle according to different solubility between the different components.
United States Patent (USP) NO.3870628 has described a kind of by from removing the bituminous method in the Residual oil of oil vacuum distilling.This method also can be used for reclaiming waste lubricating oil.
Under pressure, waste oil or distillation Residual oil are injected in the liquid propane gas with pulse method, are beneficial to oil plant is dispersed into tiny oil droplet in solvent.The oily raw material of pulsed and liquid propane gas countercurrent flow, this liquid propane gas solubilized can be used as that part of oil plant of lubricant, and makes the insoluble substance precipitation.Apply the output that mechanical vibration allegedly can improve device to device.
United States Patent (USP) NO.4265734 is the improvement of above-mentioned patent NO.3870625 method.In initial step, contaminated oil plant is injected the reservoir that propane is housed, the volume ratio that forms contaminated oil and liquid propane gas is 0.25: 5-1: 5 mixture.This mixture is left standstill about 1 hour, so that the most of contamination precipitation in the contaminated oil is to the bottom of reservoir.Then oil/propane solution is extracted out, and handled with the method among the above-mentioned patent NO.3870625.
The United States Patent (USP) NO.5286380 of Mellen relates to and removes pollutent in being reached by knacker, and Mellen is the co-inventor of this patent application.
In the patent of ' 380, useless motor oil is sent in the empty reaction vessel, make liquid fat family solvent such as liquid propane gas enter this reaction vessel then by the bottom of reaction vessel, so that oil plant mixes by 1: 10 volume ratio with solvent, wherein, pollutent is precipitated out.Then oil/solvent solution is carried out diafiltration by activated carbon beds, to remove delead and other metal pollutants.Preferred glass or plastic containers.
Traditional by removing bituminous propane extraction method in the crude oil, depend on huge product and upgrade, as produce light raw material, calculate to prove high capital contribution and high working cost.
In the reprocessing of crude oil bitumen extraction and useless motor oil, use the propane all must be in 10 as the method for solvent: 1-15: 1 ratio be used propane and oil plant, reducing soltion viscosity and proportion, thereby make trickle solid sedimentation under action of gravity of suspension fully.Needing at high proportion of this propane and oil plant makes the recovery of propane need very huge energy, and very large sedimentation container, to guarantee that very thin particle has sufficient sedimentation retention time.
The another kind of method of the useless motor oil of the reprocessing of the popular use of the U.S. is to carry out water treatment after vacuum distilling now.
In the method, waste oil is heated to about 150 ℃, to remove any moisture content and light hydro carbons.The oil plant that anhydrates that will also contain additive then is heated to about 260 ℃, to remove any diesel oil composition.
Then, oil/additive agent mixture is heated to about 370 ℃ in distillation column under about 5mmHg (definitely),, again this base oil fraction is carried out water treatment, to improve color and smell from additive, to isolate base oil.Water treatment steps also can be removed the residual poly-Polycyclic aromatic hydrocarbons of a part.
Though its purpose normally imitates to reaching, above-mentioned film vacuum distillation method has many defectives.
The subject matter of this distillation method is that additive component distilation steps to the last just is removed.In this stage, oil plant (and additive) has been heated above 370 ℃, and under this high-temperature, the thermolysis with organometallic compound is split in the pyrolysis that polymerizable compound can take place, and produces serious coking and corrosion in distillation column and utility appliance.Output efficiency has not only been disturbed in the coking of equipment and corrosion, and the quality that makes lubricating oil distillate is than all poorer under any other situation.
Though can carry out pre-treatment to waste oil with sodium hydroxide, to reduce the coking and the corrosion in device downstream zone, this need carry out the costliness upgrading to the metallurgical technology of upstream equipment, to reduce the corrosion to this zone.
Even in intermediary fraction of diesel oil post, the maintenance of equipment also is very expensive, and this is because must change column packing in every 6-8 month.
In general, calculate by the output capacity of per unit, thin-film evaporator used in the aforesaid method is very expensive on building and moving.And, in the method, there is 2% light oil (diesel oil) fraction be lost in the stage of dewatering approximately, and in the last distillation stage, still has the bituminous bottom owing to remain in, 3% the useful base oil of having an appointment again loses.
United States Patent (USP) 4624763,4624764,4661226,4634510,4627901,4622119 and 4622118 all relate to by removing wax in the lubricating oil, and it is to introduce high voltage electricity in oil/solvent mixture, to make the Wax particles nucleation before precipitation.
Australian Patent NO.605288 discloses a kind of method by extract oil in stable oil/water miscible liquid, it is the hydrocarbon solvent that adds liquefaction in emulsion, the oil plant that when leaving standstill, forms the Oil solvent phase of cutting out partial, reduce the pressure of residual biphasic system then, so that the liquid solvent of pressurization volatilization, wherein, emulsion shared oil and water.
General introduction of the present invention and purpose thereof
The purpose of this invention is to provide the method and apparatus that novel being used for removes the oil plant pollutent, they can overcome or alleviate at least some basically with existing method and/or install relevant problem.
According to an aspect of the present invention, provide a kind of by the method that removes pollutent in the oil plant, this method may further comprise the steps:
In one first pressurized vessel, in the liquid aliphatic solvent, form the solution of the oil plant of getting dirty;
Lower region at described first pressurized vessel is introduced gas with the form of tiny bubble, and wherein, described solution quilt is by the bubble agitation that rises in this solution, and pollutent is then separated from solution owing to flocculation reaction;
By separating the pollutent that has flocculated in the liquid solution; And
By separating solvent in this solution, there not to be the oil plant of pollutent basically.
Suitable solvent comprises C
1-C
7Alkane.
Solvent preferably includes liquid propane gas or butane or their mixture.
The flocculation toughener can be selected from water and/or electrolyte solution.
During flocculation reaction, the amount of water 2%v/v at least suitably in the solution of oil plant and solvent.
During flocculation reaction, the amount of water 3%v/v at least preferably in the solution of oil plant and solvent.
The concentration of water most preferably is about 3%-6%v/v in the solution of oil plant and solvent.
As the flocculation toughener, alternately and dewater outside, also can adopt ionogen as the flocculation toughener.
Suitable electrolyte comprises strong acid or highly basic.
Ionogen can be selected from H
2SO
4, HCl, NaOH or KOH.
If desired, flocculation reaction can be carried out having under conducting element and the situation that the mutual physical property of solution of oil plant and solvent contacts.
Gas can comprise polarity or non-polar gas.
Suitably, gas is selected from CO
2, N
2Or C
1-C
4Alkane.
Preferably, gas comprises propane or butane or their mixture.
Most preferably, when aliphatic solvents was propane, gas comprised propane.
The temperature of carrying out flocculation reaction is between 15 ℃-45 ℃.
The suitable temp that carries out flocculation reaction is between 15 ℃-30 ℃.
The most preferably temperature of carrying out flocculation reaction is between 18 ℃-25 ℃.
Also can may further comprise the steps by the method that removes pollutent in the oil plant:
The oil plant of the pollutent that flocculates and the solution of solvent are delivered to second pressurized vessel by first pressurized vessel;
Make in the solution of residual pollutent by oil plant and solvent and settle;
To there be the oil plant of pollutent and the solution of solvent to be delivered to the solvent stripper basically; And
Remove solvent in the solution by oil and solvent, obtain the oil plant fraction of essentially no pollutent.
If desired, the oil plant fraction of this essentially no pollutent can further come pure system by distilation steps.
Preferably, the distilation steps decompression is carried out.
Before distillation, the oil plant fraction of essentially no pollutent can pass through stripping step, to remove residual solvent and sherwood oil fraction wherein.
If desired, the pollutent resistates that is come out by first and/or second pressurized vessel can pass through stripping step, anhydrates and residual solvent to remove.
Preferably, removed the pollutent resistates that anhydrates with residual solvent and mixed, obtained flowable asphalt extender (extender) with deep fat.
Most preferably, deep fat comprises the distillation residue from distilation steps.
Contaminated oil plant can comprise automobile waste oil (drain oil).
In addition, the oil plant of getting dirty can comprise crude oil.
The oil plant of getting dirty can comprise the resistates of petroleum cracking and/or distilation steps.
In addition, contaminated oil plant can comprise hull bottom cargo tank waste oil.
Moreover the oil plant of getting dirty can comprise resulting oil/water mixture and/or oil/water miscible liquid in the oil production process.
According to a further aspect in the invention, provide a kind of refining crude oil to obtain the method for bright petroleum products, this method comprises first method according to the present invention by removing pollutent in the crude oil material, makes essentially no pollutent oil plant raw material stand follow-up purification step then.
In accordance with a further aspect of the present invention, provide a kind of method of utilizing the distillation residue in the petroleum refinement process, this method comprises the first aspect processing distillation leftover according to the present invention, separates lighter fraction then from the contaminated resistates that forms thus.
In accordance with a further aspect of the present invention, provide a kind of method of utilizing the wet oil resistates in the oil production process, this method comprises handles aqueous residue according to a first aspect of the invention, with by the oil plant fraction that wherein extracts essentially no pollutent.
According to this more on the one hand, a kind of method of utilizing cargo tank waste oil is provided, this method comprises that the method for the first aspect according to the present invention handles cargo tank waste oil, with by the fuel oil fraction that wherein extracts essentially no pollutent.
Preferably, when wet oil resistates in utilizing the oil production process and/or cargo tank waste oil, the water-content of pending oil-containing resistates at first will pass through the water extraction step, so that the water-content in the treating material is brought down below 10%.
According to a second aspect of the invention, provide a kind of being used for to remove the pollutent device by oil plant, described device comprises:
One first pressurized vessel, this container with get dirty oil plant and solvent source and, optionally, contain water and/or electrolytical flocculation toughener source phase fluid and be communicated with;
A pressurised gas source, the inlet under contiguous described first pressurized vessel of the alternative ground warp of this gas and introducing is to be dispersed in tiny bubble in oil/solvent/flocculation agent that this container comprised;
Outlet that is communicated with described inlet fluid is so that be incorporated into gas circulation in described first pressurized vessel;
A decant mouth is optionally to be removed the oil/solvent solution of essentially no pollutent by described first pressurized vessel; With
The pollutent outlet of described first a pressurized vessel bottom of vicinity is in order to optionally to remove the pollutent that is deposited in the flocculation in this lower region.
Suitable is, described device comprises one second pressurized vessel, the Oil solvent solution that accumulates the essentially no pollutent that comes out by the described first pressurized vessel decant, described second pressurized vessel comprises that an outlet and the bottom at described second pressurized vessel that is used for being extracted out continuously basically by this container the oil/solvent solution of essentially no pollutent is used to remove the outlet of accumulating the pollutent that flocculates that is deposited in wherein.
This device can comprise solvent stripping container, and to remove solvent in the oil/solvent solution by the essentially no pollutent that extracts in described first and/or second pressurized vessel, so the solvent that extracts turns back to described solvent source again.
Suitable is, described device comprises another stripping container, with by removing any residual solvent and light fuel oil fraction the material that has removed solvent that comes from above-mentioned stripping container transport.
If desired, described device can comprise distillation column, with by removing base oil product described solvent that is removed that comes from another described stripping container transport and the light fuel oil fraction.
Preferably, described device comprises a Residual oil collector, to collect the pollutent that come out by described first and second pressurized vessels.
Suitable is that described Residual oil collector can be by dividing dried up and/or residual solvent in the collected Residual oil.
If desired, described device can further comprise a Residual oil processing vessel, and this container comprises heating unit, and a flowable Residual oil material is provided.
Suitable is that described Residual oil processing vessel comprises a mixing device, so that oil plant is mixed with described Residual oil, provides flowable product.
Preferably, described device is communicated with described distillation column fluid, to provide and described Residual oil blended oil plant distillation residue.
According to a further aspect in the invention, provide a kind of device by the crude production gloss varnish, described device comprises the eradicator as second aspect present invention, with the upstream at the crude oil processing equipment of routine crude oil is carried out pre-treatment.
In accordance with a further aspect of the present invention, provide a kind of device that is used for processing the distillation residue of conventional oil water distilling apparatus, described device comprises device according to a second aspect of the invention, with by extracting valuable petroleum cuts in the petroleum tailings.
The present invention also provides another kind to be used for utilizing device by the wet oil of oil production gained.
And the present invention also provides a kind of device that is used to utilize the cargo tank waste oil that is obtained from hull bottom.
If desired, the present invention provides a kind of device that is used to handle from the oil-containing resistates of commercial and communal facility on the other hand, with by separating oil plant in waste water and/or anti-ripple water (storm water) source.
By novel device is provided, to remove pollutent such as pitch, additive and other pollutents in the waste oil: the pitch of crude oil; Pitch in the cargo tank waste oil, water and other pollutents; Or the like, the present invention has overcome or has alleviated the problems of the prior art basically.
In one embodiment, oil by pump from storage tank pump to the solvent jar, this oil plant mixes with the aliphatic solvents that comes from the solvent storage jar through another pump, as methane, ethane, propane, butane, pentane, hexane, heptane etc., adds an amount of flocculation toughener again.Advantageously, before entering the solvent jar, solvent, reagent and oil plant form oil plant, reagent and solvent mixture earlier in room temperature or be increased under about 25 ℃-40 ℃ temperature and mix.Then, with gas, preferably propane is dispersed to the bottom of solvent jar, stirs mixture with this.Can allow this stirring carry out the regular hour, after this close gas, and mixture separate via gravity promptly.
As motivating force, oil plant/propane solution is delivered to second jar with the pressure difference between two jars.Water, pitch Residual oil and some solvents are delivered to Residual oil and water separation tank by the solvent jar.
When all materials, after promptly oil plant solvent/reagent solution and water and Residual oil had all been transferred out from the solvent jar, this jar can be accepted next batch again, as waste oil and propane solvent.Oil plant/solvent solution in solution feeding jar can make those still unsegregated Residual oils in the solvent jar separate, but solution feeding jar mainly is one is installed in jar, oil plant/solvent solution is delivered to continuously solvent oil plant recovery zone (will explain later on) to this, like this, can finish a successive action.Oil plant/solvent solution is pumped by the stripping tower force (forcing) pump, and this pump increases to pressure the pressure of solvent stripping tower operation.The Residual oil that sedimentation goes out in solution feeding jar is transported to the pitch mixing tank.This time carry is that pressure difference by between two jars is finished.
Oil plant/solvent solution that Residual oil and water separator are used for being transported by the solvent pot bottom also is to separate from water from Residual oil simultaneously.Therefore, this is a three-phase (oil plant, a water and Residual oil) separator.Each phase interface determine by from specific level attitude via pump pump cross the gage glass that has porthole, other suitable observation procedures of colour-difference XOR between water and the Residual oil finish by observing again.In case observe level attitude, just water is emitted and thrown aside, or if necessary, the part of these water can be used as the flocculation toughener.Solid-state Residual oil, remaining in this solid have some propane and water, promptly is transported in the pitch mixing tank, and in this jar, Residual oil is heated, and mixes with heavy oil from the vacuum distilling column bottom.
Recyclable more than 95% of all propane solvents that is injected in the solvent jar of solvent stripping tower.Remaining propane solvent will be recovered in distillation preflash or sherwood oil flash tank.Under high pressure enter the solvent stripping tower from the oil plant/solvent solution in the solution feeding jar, this is because vane pump helps carrying.Oil plant/solvent solution promptly is introduced in the packed column in the solvent stripping tower, and wherein, oil plant and propane mixture flow through packed bed, at this, makes propane solvent by removing in the oil plant from the propane steam of the reboiler of solvent stripping tower.Propane promptly leaves the top of post, and is condenser condenses subsequently.By this condenser, propane solvent is introduced in the solvent storage jar more again, prepares against in the future needing of utilization again.
Oil plant is reduced to solvent stripping tower bottom and is entered reboiler.This reboiler uses the stream of hot oil from the distillation column bottom, and heat is provided by process furnace, then stream of hot oil is pumped through reboiler, and the heated oil material mixture is to about 260 ℃.
This deep fat material promptly is transported in the light oil flash tank that moves under low pressure more.In the sherwood oil flash tank, low pressure and high temperature make sherwood oil fraction and any propane vaporization that may be deposited in the oil plant.
The sherwood oil fraction of vaporization and propane solvent enter in the condenser of top, all are condensed at this all sherwood oil fraction.Sherwood oil fraction and propane mixture enter the sherwood oil knockout drum subsequently, rouse thus, and sherwood oil is pumped in the sherwood oil storage facility through pump.Propane flammable gas enters the two stages of compression device that has side cooler, and at this, propane solvent is compressed and sends back to the solvent storage jar.
The oil plant of flash distillation is not transported to vacuum distillation column in the sherwood oil flash tank.By reducing the pressure of oil plant,, and enter the top of distillation column still for liquid diesel oil and lubricating oil are vaporized.The liquid of vaporization is then reduced at the bottom of the tower not yet at this moment, is heated to about 350 ℃ at this, further vaporizes, and makes more oil plant vaporization.The liquid of vaporization is not transported in the deep fat circle in (hot oil loop) through pump, and wherein, this deep fat circle is taken with the pitch mixing tank for above-mentioned solvent stripping heat is provided.When by in the deep fat circle, providing these measures to make oil plant when cooling, again it is back to process furnace, at this, oil plant is heated to about 350 ℃, and returns the bottom of distillation column.
The a certain amount of heavy oil product of not vaporizing as yet in distillation column is pumped to the pitch mixing tank.Still above-mentioned deep fat material has dissolved the Residual oil from solvent jar and solution feeding jar.
The oil plant of vaporizing in distillation column passes this distillation column, and rises to certain section of post, and at this, oil plant is condensed, and is pumped to oil storage tank.Still the vaporization the sherwood oil fraction rise to post on the filled section, it is condensed at this, and is pumped away.This moment, still incondensible material, was burnt at these those steams to process furnace through sliding blade vacuum pump pump.
The present invention's these and other purpose and characteristics will become obvious by concrete description and accompanying drawing.
Brief Description Of Drawings
For understanding all respects of the present invention more completely, and it is put to reality, below with reference to preferred embodiment represented in the accompanying drawing, among the figure:
Fig. 1 is the synoptic diagram of precipitation reaction container;
Fig. 2 is the schema that is used for being removed by oil plant the device of pollutent of representing process according to the invention and device two aspects;
Fig. 3 is the enlarged diagram of bitumen extraction shown in Figure 2 system.
The detailed description of illustrated embodiment scheme
Figure 1 shows that the reaction vessel of the laboratory standard of the experimental data of being discussed after being used to produce.
Among Fig. 1, container 201 comprises transparent cylindrical acrylplastics wall 202, and it has top closure member 203 and is generally the conical closed bottom member 204 of frustum.Expansible mild steel webmaster 205 is positioned within the container 201, and is movably, and its effect will make an explanation afterwards.
The base portion of container 200 is asphalt valves 206, and in order to removing the pitch Residual oil 207 that accumulates in this zone, and another valve 208 is arranged on the conduit 209 that is connected with waste oil and other source of additive (not shown).
Two-way valve 209 with petrogas or pressurized gas such as CO are provided
2Or N
2The conduit 210 of source (not shown) is communicated with.Valve 209 also is communicated with gas recirculation system, and this system is included in the conduit 211 that links to each other with container 1 top in the fluid communication, segregaion valve 212, gas compression device 213 and heat exchanger 214.Gas is dispersed in the container 201 through spraying house steward 217, and described house steward 217 has a plurality of nozzles 218, so that gas dispersion is become tiny bubble.
The outflow conduit 215 that has segregaion valve 216 is connected on solvent stripping tower/recovery system (not shown).
The method of preferred aspect comprises according to the present invention, with 1: 3-1: 6 ratio is mixed the moisture and/or electrolytical oil plant of getting dirty with petrogas, at room temperature use tiny bubble spray mixture 10-20 minute of propane then, make the about 10-20 of mixture sedimentation minute afterwards.
Composite liberation becomes three different layers, transparent oil plant/propane layer, water layer and residual layer.Collect each layer, and from transparent oil plant fraction, remove propane.Embodiment
The 1000ml oil plant of packing in the reaction vessel of Fig. 1 is sneaked into liquid propane gas in 1: 6 ratio then.By propane flammable gas was pumped into liquid form mixt 10 minutes with the tiny bubble form, stir propane/fuel mixture.
Spraying produces the bubble of high flow rate, and the diameter of these bubbles is 1-3mm, and mixing effect light and slow relatively but turbulence can be provided.After stirring 10 minutes, make the mixture sedimentation, and measure subsidence rate.
After all complete sedimentation of the solid that suspends, remove transparent oil plant/propane mixture layer, under reduced pressure from this mixture, extract propane then.Remove still residue, and its propane of carrying secretly is under atmospheric pressure cooked out.
Used oil plant is an automobile waste oil in test, and its initial water content is 3.8%.This oil plant is heated to 140 ℃ of dehydrations, makes water-content be lower than 0.2%, proportion is 0.887kg/m
3
In oil plant and solvent ratio is that 1: 10 ratio is diluted in oil plant in the hexane, measures the transparency that is removed oil plant.
Resistates in the weighing test, and, measure the water-content of resistates again with the ASTM method of standard with naked eyes comparison viscosity and flow characteristics.
All liquid additive in the oil plant are as H
2O, 97%H
2SO
4, 35%HCl and red water all is in v/v, and 45%KOH, CH
3COOH, the adding of clay and Sodium hexametaphosphate 99 is all in wt/v.
In the test carried out, during stirring, all have throw out to form with bubble flow.After gas atomization stopped, because the bubble of carrying secretly passes liquid, the slight mixing of liquid mixture/throw out suspended substance was also being carried out, and throw out just may continued growth.
Following table shows the effect of water in oil plant/propane mixture of different concns, and ionogen and the effect of other chemical substances in the settling property of handled oil plant and resistates.
Table I
The effect (metallic screen arranged) of water-content in the dehydration oil plant
| Water-content (%) | Subsidence rate (min) | Oil plant pigment | Resistates (gm) | Water in the resistates (%) |
| ＜0.2 | Very slow 14-18 | ????8.0 | No solid residue 25mm oil plant/sludge | ????N/A |
| ??1.0 | Slow 8-9 | ????7.5 | No solid residue 12mm oil plant/sludge | ????N/A |
| ??2.0 | Slow 8-9 | ????7.0 | No solid residue 12mm oil plant/sludge | ????N/A |
| ??3.0 | Medium 5-6 | ????7.0 | ????40-51 | ????40 |
| ??5.0 | Medium 5-6 | ????7.0 | ????45-66 | ????70 |
| ??20.0 | Medium 5-6 | ????7.0 | ????7200 | ????64 |
Table I A
The effect (removal metallic screen) of water-content in the dehydration oil plant
| Water-content (%) | Subsidence rate (min) | The oil plant color | Resistates (gm) | Water in the resistates (%) |
| ????5.0 | Very slowly＞30 | ???7.5 | No solid excess 50mm oil plant/sludge | N/A |
Table II
The effect (metallic screen arranged) of KOH in the dehydration oil plant
| KOH(％) | Subsidence rate (min) | Oil plant pigment | Resistates (gm) | Water in the resistates (%) |
| ＜0.2 | Very fast 2-3 | ??5.5 | 28 viscosity | ????12 |
| ??0.5 | Very fast 2-3 | ??4.5 | 36 viscosity | ????16 |
| ??0.5 | Fast 3-4 | ??5.5 | 19 viscosity | ????30 |
Table II A
The effect (removal metallic screen) of KOH in the dehydration oil plant
| ???KOH(％) | Subsidence rate (min) | Oil plant pigment | Resistates (gm) | Water in the resistates (%) |
| ????0.5 | Very fast 2-3 | ????7.5 | 65 viscosity | ????12 |
Table III
The effect of acid in the dehydration oil plant
| Concentration (%) | Subsidence rate (min) | Oil plant pigment | Resistates (gm) | Water in the resistates (%) |
| 0.2H 2SO 4(98％) | Very fast 2-3 | ??4.5 | 21 is very sticking | ????6 |
| 0.5H 2SO 4(98％) | Fast 3-4 | ??4.5 | 30 is very sticking | ????9 |
| 0.5HCl (35％) | Medium 8-10 | ??4.0 | 39 is very sticking | ????21 |
| 0.5 CH 3COOH | Slow 10-12 | ??6.5 | 29 is sticking | ????3.5 |
Table IV
The effect of different chemical material in the dehydration oil plant
| Concentration (%) | Subsidence rate (min) | Oil plant pigment | Resistates (gm) | Water in the resistates (%) |
| 1%Calgon+1% water | Fast 3-4 | ????5.5 | 120 is sticking | ????30 |
| 0.5% hexametaphosphate+2% water | Very slow 20-25 | ?????- | 34 is sticking | ????27 |
| 5% red water | Slow 8-10 | ????7.5 | 47 is sticking | ????- |
| ?5％CH 3OH | Very slow 10-25 | ????10 | No solid residue | ????N/A |
| 5% clay | Slow 8-10 | ????7.5 | ????65* | ????13 |
* at first sedimentation of some clays is that clay and resistates are with the sedimentation of magma form then.
The above results shows have the macrobead of many factor pairing energy rapid subsidence in propane/fuel mixture to work.Also show have many strong mechanism all to can be used to illustrate big flocculation agent particulate and form.
And the essence of the various strong mechanism of no-trump is limited to the meaning of any hypothesis, below discusses and just attempts to explain observed basic to they various phenomenons.
Except that Van der Waals force and electrical double layer repulsion, the stability of the surfactant mixture/dispersion of complexity also is subjected to the influence of multiple other factors, as absorbing energy, entropy energy and bridged bond energy.
If at waste oil is simply in about 1: the waste oil of 3-1: 4v/v there is no tangible pollutent cohesion or precipitation when mixing with liquid propane gas with the liquid propane gas ratio, the introducing of bubble so, particularly having under water or the electrolytical situation, can make solution/dispersion lose stable situation increases.This propane facture with prior art is opposite fully, and it is 1 that the method for prior art needs oil plant/liquid propane gas ratio: 10-1: 15, and to reduce the viscosity and the proportion of solution, make fine particle solid and insoluble oil plant could precipitate through the very long settling time.
In the methods of the invention, owing to introduce the propane bubble, and propane flammable gas is taken away and recirculation by the upper area of reaction vessel, so the ratio of oil plant/liquid propane gas does not have big variation.
With other gases such as CO
2And N
2Test show, though effect not as good as propane, under the situation that has water and/or ionogen to exist, the body of these gas stirs oil plant/propane mixture also can cause aggegation or flocculation reaction.Therefore, the form that the dispersion of tiny bubble in oil plant/propane mixture can electrostatic double layer produces triboelectric charge at bubble surface.
If waste oil is the mixture of ionic species such as organic metallic compound and non-ionic type macromolecular substance such as synthesized polymer viscosity index improver and polarity and non-polar molecule material, it is believed that the mixture of the character of waste oil like lyophily and lyophobic colloid system.Still inexplicable effect that this forms solid by metallic screen and strong electrolyte are confirmed the effect of this process.When balance, the character of this system and lyophobic colloid system class seemingly in the latter, are added relatively and can be played flocculation than ionogen in a small amount.Strictly speaking, though water is not ionogen, it is believed that the oil plant of getting dirty contains water-soluble impurity, these impurity promptly play similar electrolytical effect.
By checking the characteristic of aggegation/flocculation reaction, can obtain the subsidence rate of solids and by the essence of the solids that is added into the various chemical substance gained in the dehydration oil plant, and the complicacy of process is had certain understanding.Water
Without any other chemical substances the time, water plays crucial effects in forming big residue particles.If oil plant is (＜0.2%) done, the size of formed insoluble residue is very little, can not flocculate and sedimentation very slow.Settled resistates does not form the viscous substance that remains in the column bottom, but concentrates in oil plant/propane mixture, and when propane is removed, can be dissolved in the oil plant again.
The ratio of propane and oil plant is 6: 1, before subsidence rate reaches considerable change, needs at least 3% water in the oil plant.When this concentration, can form bigger residue particles, and resistates can be separated from oil plant/propane mixture at an easy rate.Resistates is a viscosity, and can have the structure of similar tar.Do not carry out viscosity measurement.Increase at water-content and to be higher than at 3% o'clock, the subsidence rate of resistates is still kept constant, but increases with water-content, and the subsidence rate of resistates also can increase.This mainly is owing to be combined in the increase of the water in the resistates.
For forming these larger particles, need the water of enough droplet-shaped, like this, the insolubles that is settled out can be attached on them.The minimum level of water that this task found may be because the solubleness of water in propane-fuel mixture, and if the water-content in the oil plant inaccessible 3.0%, just can not obtain competent nuclear.Though the bubble of triboelectrification can form nuclear with the ability of itself, it is believed that between bubble and particle water charge transfer can take place what water/ionogen this just may be interpreted as and endorse the raising flocculation rate.
But when not having metallic screen in reactor, the oil plant that contains 5.0% water can not form macrobead, and can be with the mode sedimentation similar to the drier oil material.Particle size is little, sedimentation very slowly, and can not produce and be easy to isolating resistates from oil plant-propane mixture.
It is believed that metallic screen provides conductive base in non-conductive medium, this helps electric charge to shift between bubble and aqueous electrolyte or mixture intermediate ion and polar molecule material.
Because the insoluble residue that produces in the drier oil material can not form the resistates of rapid subsidence, so the existence of water and metal (iron or copper) sieve is necessary for forming macrobead.Most possible mechanism is, the turbulence that is produced by the propane spraying mixes can produce triboelectric charge on water droplet, and this makes the precipitation resistates be attracted and be attached on the droplet, or electric charge on the bubble band is given water droplet with this charge transfer then.
Mix the water droplet-particle contact that also can provide bigger, and this helps to overcome double-deck the repulsion.Because the existence of metallorganics, resistates will have tangible ionic charge, but these can not be interpreted as the metallic surface what needs the mixture contact.
Metal all keeps inertia in whole process, and do not have the visible sign show its reaction or the corrosion.The described testing apparatus of Fig. 2 and Fig. 3 comprises the mild steel reaction vessel, and moves in the mode identical with the lab investigation that have metallic screen.Alkali
When not having water, in the drier oil material, add 45%KOH solution and can produce resistates big, that sedimentation is fast.Compare with the above-mentioned oil plant for preparing in the method for water, color increases significantly, and sedimentation is faster, and the viscosity of settled resistates significantly increases.
3% water adds that 0.5%KOH can reduce subsidence rate (but being better than when having only 3% water) slightly, and the viscosity of resistates is descended.Because the existence of KOH, the water-content in the resistates is reduced.
When using KOH, having or not of the formation of the resistates of rapid subsidence and metallic screen is irrelevant.This shows, the different mechanism of a kind of mechanism when having only water is affecting the formation of big residue particles.The increase of resistates viscosity shows more bonding or crosslinked has taken place.
Highly basic and resistates reaction, thus when owing to strong mixing particle being in contact with one another, these particles are easy to be attached together mutually.Although also do not know to have taken place on earth what reaction, the effect of KOH and NaOH is all similarly good, and ammoniacal liquor and Ca (OH)
2Then not all right.
Do not have the test of metallic screen to produce more substantial resistates, and the color of oil plant is darker.Acid
When not having water, 0.2% or 0.5% sulphuric acid soln has produced big sedimentation resistates.Oil plant color identical during with 0.5%KOH.But resistates all is at present the most sticking, this show have considerable crosslinked.The existence of water has weakened the degree of depth of reaction in the oil plant.
Similarly, when using 0.5%HCl, subsidence rate is medium, but fast when having only water to exist.Yet the oil plant color but is best in all tests.Because the solution of acid 35%, the water-content of this task is 2%.Can find out that by former work this will reduce settling velocity.
Weak acid such as acetate produce the slow resistates of sedimentation, and this resistates is difficult to by separating in oil plant-propane mixture.
Strong acid can be had an effect in the mode similar to highly basic, is easy to attached to the material on other residue particles by forming with the resistates reaction, or produces crosslinking reaction between particle.Bronsted lowry acids and bases bronsted lowry also can increase the amount of insolubles by precipitation metal hydroxides and vitriol.
For this type system, the spraying of propane or other gas just is not crucial, and can reach similar result by mechanically mixing yet.Dispersion agent
Calgon, a kind of commercially available water treatment additive demonstrates different effects with Sodium hexametaphosphate 99.The Calgon of high density (1%) and the resistates of 5% water generates rapid subsidence and the oil plant of medium color.Sodium hexametaphosphate 99 in 2% water produces settled at a slow speed resistates, and this resistates is different with the test of having only 2% water, can be by separating in propane-fuel mixture.
These two kinds of compounds all are as the particle dispersants in the aqueous system, test they be attempt to stop water with, resistates combines.As if this has obtained the success of part, and the existence of high charge ion has strengthened the growth of residue particles.This may be because the precipitation of metal phosphate.Other chemical substances
The interpolation of clay and red water does not obviously change the particle size and the subsidence rate of resistates.Clay has improved settling character by adsorbing some resistatess in its surface.Resistates is more dried and mobile poor.
No matter be to be used for automobile waste oil, thick crude oil, petroleum tailings, or cargo tank waste oil etc., find that method of the present invention can remove pollutent to 95% in the initial flocculation stage, this comprises water.In follow-up stripping and/or distillation stage, find light fuel oil fraction and base oil fraction contamination-free basically.
Fig. 2 schematically shows the commercial device that is used for removing from oil plant pollutent.
In Fig. 2, this device comprises first pressurized vessel 10 that is used to accept the solvent and the formation solution of the oil plant of getting dirty, this first pressurized vessel 10 has top and bottom 12 and 14 respectively, the bottom 14 be used for by pipeline 15 with gas dispersion in the solution of first pressurized vessel 10, retrieving arrangement with solvent stripping tower 16 forms, at this, solution is divided into the solvent and the oil plant of vaporization, and gasifying solvent is sprayed by the bottom 14 of first pressurized vessel 10 by pipeline 15 again and introducing again.
This device also comprises get dirty oil plant such as the waste vapour oil supplying device 18 that is communicated with the first pressurized vessel gas by waste oil pipeline 20 and valve 22, and waste vapour oil charge pump 24 is with waste vapour oil pump to the first pressurized vessel 10.In addition, this device also comprises the supply 26 that is introduced into the liquid solvent in first pressurized vessel 10 through liquid solvent pipeline 28 and valve 30, and liquid solvent pump 32 is used for liquid solvent by supply 26 device pumps to container 10.
Advantageously, feed- stock pipeline 20 and 28 middle portion form the 3rd pipeline 34 that leads to container 20, and like this, the 3rd pipeline 34 is just introduced liquid solvent and waste vapour oil in the container 10 simultaneously, formation solution.Inlet 152 is optionally introduced the flocculation toughener.
In addition, this device comprises second pressurized vessel 36 that is communicated with first container, 10 fluids by pipeline 38, and this second container 36 comprises top and bottom 40 and 42 respectively.Advantageously, remove solvent and oil plant in the solution, and then they are introduced second container 36 by the pressure difference between two containers by first container 10.
This device further comprises solution, and pitch Residual oil and water separation tank 44, this jar comprise the inlet 46 that is communicated with container 10 fluids, at this, by pump 48 solvent in the solution and oil plant, pitch Residual oil and water is delivered to separating tank 44 by bottom 14.Separating tank 44 also comprises first outlet 50, and water mouth is thus removed from jar 44, second outlet 52, and pitch Residual oil mouth is thus removed from jar 44 and the 3rd outlet 54, and solvent in the solution and oil plant mouth thus are returned to first container 10.The inside of jar 44 is provided with spillway 56 (not shown) and water outlet 50, and water and solvent are by flowing through on the above-mentioned spillway 56.
This device further comprises pitch Residual oil mixing tank 60, and this jar comprises the inlet 62 that is communicated with second outlet, 52 fluids of jar 44, through pipeline 64, collects the pitch Residual oils by this inlet 62, and the outlet 66 of removing bitumen product.Advantageously, the bottom of container 36 42 is communicated with inlet 62 fluids of mixing tank 60 by pipeline 68, thus with other pitch Residual oil by removing in the container 36.
As mentioned above, this device comprises solvent stripping tower 16, and this stripping tower connects energy as retrieving arrangement by pipeline 70 and second container, 36 fluids.Comprise charge pump 72 in the pipeline 70, be beneficial to solvent and oil plant solution are delivered to stripping tower 16.And this charge pump 72 has increased the pressure difference between container 36 and the stripping tower 16.Preferably, stripping tower 16 comprises solvent and oil plant solution at lining mobile packed column 74, and post 74 has top and bottom 76 and 78 respectively, and top 76 comprises outlet 80, and the solvent of most heating vaporization is discharged from stripping tower 16 by this outlet.Stripping tower 16 comprises that further integral body is connected to the reboiler 82 bottom 78 and that be connected with this bottom flow of post 74, and reboiler 82 comprises outlet 84, and by this outlet, oil plant and the solvent that remains are discharged from stripping tower 16.
This device also comprises condenser 86, and this condenser is communicated with the top 76 and solvent supplier 26 fluids of packed column 74 by pipeline 88, and thus, the solvent of heating vaporization is condensed into liquid form, and is put back to needing in order to future in the solvent supplier 26 again.
This device further comprises gasoline flash drum 90, this drum has corresponding top and bottom 92 and 94, top 92 comprises outlet 96, and bottom 94 comprises outlet 98, drum 90 is by pipeline 100 and reboiler 82 fluid communication, like this, oil plant and remaining solvent can be transported to gasoline flash drum 90 by the solvent stripping tower.
This device comprises that also another passes through the condenser 102 that pipeline 104 is communicated with top 92 fluids of drum 90, is condensed into liquid at the gasoline of this vaporization.This device further comprises gasoline collection drum 106, this drum has top and bottom 108 and 110 respectively, top 108 comprises solvent outlet 112, and bottom 110 comprises the outlet 114 of liquid gasoline, drum 106 is communicated with condenser 102 fluids by pipeline 116, like this, gasoline and solvent can be delivered to drum 106 by condenser 102.This device also comprises the petrol-feed pump 114 that is communicated with outlet 114 fluids of drum 106, thus, and being pumped in the gasoline supply (not shown) of purified gasoline products.
This device further comprises two groups of compressors and the intermediate water cooler 122 that is communicated with outlet 112 fluids in the drum 106 by pipeline 124, like this, the solvent in the drum 106 thus by and further compressed and cooled off.Compressor and water cooler 122 are communicated with condenser 86 fluids by pipeline 126, and the solvent that passes through so thus is condensed and returns the usefulness of solvent supplier 26 in order to future.Middle rank sucks washer (not shown) contiguous water cooler and compressor 122 and also is in fluid communication with it, and like this, is returned to drum 106 at the liquid of this condensation.
This device also comprises vacuum distillation column 128, this post has top, middle part and bottom 130,132 and 134 respectively, top 130 comprises the outlet 136 of refined diesel oil fuel product, middle part 132 comprises the outlet 138 of bright stock product, and bottom 134 comprises the outlet 140 of heavy oil and distillation residue, and post 128 is communicated with outlet 98 fluids in the drum 90 by pipeline 142.This device further comprises process furnace 144, is used for the oil plant of heated beam 128.And post 128 is communicated with by inlet 62 fluids of pipeline 146 with jar 60, and thus, the heavy oil distillation residue of heating are introduced in the jar 60, to mix with the pitch Residual oil, form final asphaltic products..Bitumenpump 148 preferred Residual oil capable of circulation and oil plants are beneficial to mix.Pipeline 150 is arranged between jar 60 and the condenser 102, like this, and can be by removing unnecessary solvent vapour and water in the jar 60.
Can be with the flocculation toughener by being introduced into first pressurized vessel 10 through intake 152 in the suitable storing unit (not shown).The reagent that the toughener that flocculates can comprise that water, strong electrolyte and strong acid or alkaline earth metal hydroxides or other are suitable or the aqueous solution of their mixture.
If desired, but one of through port 152 and 156 or both introduce NaOH or KOH, to improve the color of refining base oil product.
The tentative operation of long-time running shows, separation, stripping, boils or the efficient of vacuum distilling container does not reduce or changes again, and except that the pitch mixing tank has the tar rusty stain, almost do not have evidence to show that any parts of device produce coking or corrosion in other words.
Figure 3 shows that another embodiment of the pitch Residual oil system of processing that is shown among Fig. 2, for clarity sake, all adopt identical label.
Because when cooling off under normal pressure, the Residual oil that is come out by propane extraction unit 44 is to contain water and the solid matter of the propane gas of being carried secretly, thus it be not suitable for selling as the by-product mouth, and its processing of discarding is very difficult.
The method according to this invention is mixed the mixture of heavy oil resistates with viscosity Residual oil, water and propane, the former is from vacuum distillation column 128, and the latter's mixture is that two bursts of logistics from propane extraction vessel 44 and container 36 process conduits 146 and 64/68 are pumped into by static pump 300.Then with mixture through over-heat-exchanger 301, at this, the temperature of mixture rises to about 150 °.
The mixture of heating flows to the inlet 303 that links to each other with extraction vessel 304 through conduit 302.With the fog-spray nozzle 305 that is communicated with of inlet 303 fluids mixture is sprayed into film pouring out on the dish (Shed tray) 306, with increase propane and water vapor separating by mixture.Outlet 307 is communicated with conduit 150 (Fig. 2) fluid, with recovery and separating propane and water vapour
Residual oil/fuel mixture through export 308 and bitumenpump 309 leave container 304, and be dispersed into anhydrous and viscous liquid propane by conduit 310, this just can be used as marketable product, as the pitch weighting agent of roof, shop or usefulness such as pave the way.
Though remove pollutent with reference to reaching in vehicle lubricating oil or " waste oil " by knacker, method and apparatus to the present invention is illustrated, but concerning coming the field skilled person, do not changing or only doing under the situation of some changes, obviously this method and apparatus also can be used for by removing pollutent in other oil plants.
For example, this method can be used on the upstream of petroleum cracking/water distilling apparatus, with by removing pitch and other pollutents in the raw material, these pollutents can wait and reduce lysis efficiency by poisoning catalyzer, or reduce the efficient of vacuum distilling step, cause too early coking and corrosion in distillation column.
Similarly, the resistates in conventional cracking/distillating method also can be handled according to the present invention, and is valuable to extract, but can not be by the lighter fraction that extracts economically in the resistates.
The all right hull bottom cargo tank waste oil of the present invention, the oiliness refuse and the emulsion that produce during Tertiary crudes extracts, and reclaim valuable hydrocarbon economically in oil refuse that in seabed crude oil extracts, produces and the emulsion.
But the byproduct in inventive method is the sell goods as asphalt extender, and heavy metal and other toxicants have been extracted in the oil plant of getting dirty, but the asphalt extender material is the bonding matrix of safe, non-water lixiviate, this can avoid requisite with expensive and with the relevant danger of other devices that is used to dispose toxic pollutants.
If desired, base oil product prepared in accordance with the present invention is even further also can be upgraded with known hydroprocessing process.
Concerning the one skilled in the art, it is equally clear, not departing under essence of the present invention and the scope, method and apparatus of the present invention can be made improvements and change.
Claims (50)
1, a kind of by the method that removes pollutent in the oil plant, this method may further comprise the steps:
In one first pressurized vessel, in the presence of the flocculation toughener, in the liquid aliphatic solvent, form the solution of the oil plant of getting dirty;
Lower region at described first pressurized vessel is introduced gas with the form of tiny bubble, and wherein, described solution quilt is by the bubble agitation that rises in this solution, and pollutent is then separated from solution owing to flocculation reaction;
By separating the pollutent that has flocculated in the liquid solution; And
By separating solvent in this solution, there not to be the oil plant of pollutent basically.
2, method as claimed in claim 1, wherein solvent comprises C
1-C
7Alkane.
3, method as claimed in claim 2, wherein solvent preferably includes liquid propane gas or butane or their mixture.
4, as each method in the claim 1 to 3, the toughener that wherein flocculates can be selected from water and/or electrolyte solution.
5, method as claimed in claim 4, wherein, during flocculation reaction, the amount of water 2%v/v at least suitably in the solution of oil plant and solvent.
6, method as claimed in claim 5, wherein, during flocculation reaction, the amount of water 3%v/v at least preferably in the oil plant of oil plant and solvent and the solvent solution.
7, method as claimed in claim 6, wherein, the concentration of water is in the scope of about 3%-6%v/v in the solution of oil plant and solvent.
8, the method for each claim as described above wherein uses ionogen as the flocculation toughener.
9, method as claimed in claim 8, wherein, ionogen comprises strong acid or highly basic.
10, method as claimed in claim 9, wherein, ionogen can be selected from H
2SO
4, HCl, NaOH or KOH.
11, the method for each claim as described above, wherein, flocculation reaction can be carried out under conducting element and the situation that the mutual physical property of solution of oil plant and solvent contacts having.
12, the method for each claim as described above, wherein, gas can comprise polarity or non-polar gas.
13, as the method for claim 12, wherein, gas is selected from CO
2, N
2Or C
1-C
4Alkane.
14, as the method for claim 13, wherein, gas comprises propane or butane or their mixture.
15, as the method for claim 14, wherein, when aliphatic solvents was propane, gas comprised propane.
16, the method for each claim as described above, wherein, flocculation reaction is to carry out under the temperature between 15 ℃-45 ℃.
17, as the method for claim 16, wherein, flocculation reaction is to carry out under the temperature between 15 ℃-30 ℃.
18, as the method for claim 18, wherein, flocculation reaction is to carry out under the temperature between 18 ℃-25 ℃.
19, the method for each claim as described above wherein, also can be may further comprise the steps by the method that removes pollutent in the oil plant:
The oil plant of the pollutent that flocculates and the solution of solvent are delivered to second pressurized vessel by first pressurized vessel;
Make in any residual solution of pollutent and settle by oil plant and solvent;
To there be the oil plant of pollutent and the solution of solvent to be delivered to the solvent stripper basically from second pressurized vessel; And
Remove solvent in the solution by oil and solvent, obtain the oil plant fraction of essentially no pollutent.
20, the method for each claim as described above, wherein, the oil plant fraction of essentially no pollutent can further come pure system by distilation steps.
21, as the method for claim 20, wherein, distilation steps under reduced pressure carries out.
22, as the method for claim 20 or 21, wherein, before distillation, the oil plant fraction of essentially no pollutent can pass through stripping step, to remove residual solvent and sherwood oil fraction wherein.
23, the method for each claim as described above, wherein, the pollutent resistates that is come out by first and/or second pressurized vessel can pass through stripping step, anhydrates and any residual solvent to remove.
24, as the method for claim 23, wherein, removed the pollutent resistates that anhydrates with residual solvent and mixed, obtained flowable asphalt extender with deep fat.
25, as the method for claim 24, wherein, deep fat comprises the distillation residue from distilation steps.
26, the method for each claim as described above, wherein, contaminated oil plant comprises automobile waste oil.
27, as each method in the claim 1 to 25, wherein, the oil plant of getting dirty can comprise crude oil.
28, as each method in the claim 1 to 25, wherein, the oil plant of getting dirty comprises the resistates of petroleum cracking and/or distilation steps.
29, as each method in the claim 1 to 25, wherein, contaminated oil plant can comprise hull bottom cargo tank waste oil.
30, as each method in the claim 1 to 25, wherein, the oil plant of getting dirty comprises resulting oil/water mixture and/or oil/water miscible liquid in the oil production process.
31, a kind of refining crude oil to be obtaining the method for bright petroleum products, and this method comprises according to each method in the claim 1 to 25 makes essentially no pollutent oil plant raw material stand follow-up purification step by removing pollutent in the crude oil material then.
32, a kind of method of utilizing the distillation residue in the petroleum refinement process, this method comprise according to each method in the claim 1 to 25 handles distillation leftover, separates lighter fraction then from the contaminated resistates that forms thus.
33, a kind of method of utilizing the wet oil resistates in the oil production process, this method comprise according to as each method processing aqueous residue in the claim 1 to 25, with by the oil plant fraction that wherein extracts essentially no pollutent.
34, a kind of method of utilizing cargo tank waste oil, this method comprise according to as each method processing cargo tank waste oil in the claim 1 to 25, with by the fuel oil fraction that wherein extracts essentially no pollutent.
35, as claim 33 ' or method of 34, wherein, preferably, when wet oil resistates in utilizing the oil production process and/or cargo tank waste oil, the water-content of pending oil-containing resistates at first will pass through the water extraction step, so that the water-content in the treating material is brought down below 10%.
36, a kind of being used for removes the pollutent device by oil plant, and described device comprises:
One first pressurized vessel, this container with get dirty oil plant and solvent source and, optionally, contain water and/or electrolytical flocculation toughener source phase fluid and be communicated with;
A pressurised gas source, the inlet under contiguous described first pressurized vessel of the alternative ground warp of this gas and introducing is to be dispersed in tiny bubble in oil/solvent/flocculation agent that this container comprised;
Outlet that is communicated with described inlet fluid is so that be incorporated into gas circulation in described first pressurized vessel;
A decant mouth is optionally to be removed the oil/solvent solution of essentially no pollutent by described first pressurized vessel; With
The pollutent outlet of described first a pressurized vessel bottom of vicinity is in order to optionally to remove the pollutent that is deposited in the flocculation in this lower region.
37, as the device of claim 36, comprise one second pressurized vessel, the Oil solvent solution that accumulates the essentially no pollutent that comes out by the described first pressurized vessel decant, described second pressurized vessel comprises that an outlet and the bottom at described second pressurized vessel that is used for being extracted out continuously basically by this container the oil/solvent solution of essentially no pollutent is used to remove the outlet of accumulating the pollutent that flocculates that is deposited in wherein.
38, as the device of claim 37, further comprise solvent stripping container, to remove solvent in the oil/solvent solution by the essentially no pollutent that extracts in described first and/or second pressurized vessel, so the solvent that extracts turns back to described solvent source again.
39,, comprise another stripping container, with by from the material that has removed solvent that above-mentioned stripping container transport is come, removing any residual solvent and light fuel oil fraction as the device of claim 38.
40, as the device of claim 39, comprise distillation column, with by removing base oil product described solvent that is removed that comes from another described stripping container transport and the light fuel oil fraction.
41, as each device in the claim 37 to 40, comprise a Residual oil collector, to collect the pollutent that comes out by described first and second pressurized vessels.
42, as the device of claim 41, wherein, described Residual oil collector can be by dividing dried up and/or residual solvent in the collected Residual oil.
43, as the device of claim 42, wherein, described Residual oil processing vessel comprises heating unit, and a flowable Residual oil material is provided.
44, as the device of claim 43, wherein, described Residual oil processing vessel comprises a mixing device, so that oil plant is mixed with described Residual oil, provides flowable product.
45, as the device of claim 44, wherein, described device is communicated with described distillation column fluid, to provide and described Residual oil blended oil plant distillation residue.
46, a kind of device by crude production gloss varnish (bright oil), described device comprise as each decontamination device in the claim 37 to 45, with the upstream at the crude oil processing equipment of routine crude oil carried out pre-treatment.
47, a kind of device that is used for processing the distillation residue of conventional oil water distilling apparatus, described device comprise according to each device in the claim 37 to 46, with by extracting valuable petroleum cuts in the petroleum tailings.
48,, be used for utilizing wet oil by the oil production gained according to each device in the claim 337 to 45.
49, according to each device in the claim 37 to 45, be used to utilize the cargo tank waste oil that is obtained from hull bottom.
50,, be used for handling oil-containing resistates, with by separating oil plant in waste water and/or the anti-ripple water source from commercial and communal facility according to each device in the claim 37 to 45.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US19747294A | 1994-02-15 | 1994-02-15 | |
| US08/197,472 | 1994-02-15 |
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|---|---|
| CN1143383A true CN1143383A (en) | 1997-02-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95191643A Pending CN1143383A (en) | 1994-02-15 | 1995-02-14 | Removing contaminants from oil |
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|---|---|
| EP (1) | EP0745113A4 (en) |
| JP (1) | JPH10500147A (en) |
| CN (1) | CN1143383A (en) |
| AU (1) | AU700298B2 (en) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104729949A (en) * | 2013-12-23 | 2015-06-24 | 北京橡胶工业研究设计院 | Analysis method for contaminativity of antioxidant to solvent system |
| CN115003783A (en) * | 2020-01-24 | 2022-09-02 | 伊特利姆再生公司 | Improvement of by-products of waste oil regeneration process |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2140989B1 (en) * | 1995-08-02 | 2000-08-16 | Sener Ing & Sist | PROCEDURE TO GENERATE ELECTRIC ENERGY FROM USED OILS AND OTHER WASTE OF OIL. |
| GB2335436B (en) * | 1998-03-04 | 2002-05-15 | Olim Technologies Sa | Method of refining waste oil |
| CN103555367A (en) * | 2013-11-25 | 2014-02-05 | 辽宁中旭石油化工有限公司 | Method for producing naphtha, diesel oil and lubricant base oil by using used lubrication oil |
| CN104927918B (en) * | 2015-06-12 | 2016-12-07 | 中国石油大学(华东) | A kind of waste lubricating oil produces the combination regeneration method of top-grade lubricating oil product |
| CN107653053A (en) * | 2017-09-26 | 2018-02-02 | 新乡市恒星科技有限责任公司 | A kind of high lubricating grease preparation facilities of automaticity |
| US10596487B2 (en) * | 2017-09-27 | 2020-03-24 | Rj Lee Group, Inc. | Methods and apparatus for clarification of pyrolysis oils |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4169044A (en) * | 1977-07-21 | 1979-09-25 | Phillips Petroleum Company | Re-refining used lube oil |
| US4214975A (en) * | 1978-05-10 | 1980-07-29 | The Lummus Company | Solvent recovery process for processing of hydrocarbons |
| US4354928A (en) * | 1980-06-09 | 1982-10-19 | Mobil Oil Corporation | Supercritical selective extraction of hydrocarbons from asphaltic petroleum oils |
| US4824555A (en) * | 1987-07-09 | 1989-04-25 | The Standard Oil Company | Extraction of oil from stable oil-water emulsions |
| CA1310289C (en) * | 1988-11-01 | 1992-11-17 | Mobil Oil Corporation | Pipelineable cyncrude (synthetic crude) from heavy oil |
| US5000838A (en) * | 1989-12-13 | 1991-03-19 | Mobil Oil Corporation | Low efficiency deasphalting and catalytic cracking |
| US5286380A (en) * | 1990-05-14 | 1994-02-15 | Petroleum Technology Corporation | Apparatus for contaminated oil reclamation |
-
1994
- 1994-04-29 GB GB9408609A patent/GB9408609D0/en active Pending
-
1995
- 1995-02-13 IL IL11262395A patent/IL112623A/en not_active IP Right Cessation
- 1995-02-14 CA CA002183433A patent/CA2183433A1/en not_active Abandoned
- 1995-02-14 RU RU96118411A patent/RU2140433C1/en active
- 1995-02-14 CN CN95191643A patent/CN1143383A/en active Pending
- 1995-02-14 WO PCT/US1995/001861 patent/WO1995021902A1/en not_active Application Discontinuation
- 1995-02-14 EP EP95911730A patent/EP0745113A4/en not_active Ceased
- 1995-02-14 JP JP7521409A patent/JPH10500147A/en active Pending
- 1995-02-14 TW TW084101331A patent/TW265271B/zh active
- 1995-02-14 AU AU19191/95A patent/AU700298B2/en not_active Ceased
- 1995-02-14 BR BR9506794A patent/BR9506794A/en not_active Application Discontinuation
- 1995-02-15 ZA ZA951225A patent/ZA951225B/en unknown
- 1995-02-15 EG EG13195A patent/EG20462A/en active
- 1995-02-15 CO CO95005816A patent/CO4410379A1/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104729949A (en) * | 2013-12-23 | 2015-06-24 | 北京橡胶工业研究设计院 | Analysis method for contaminativity of antioxidant to solvent system |
| CN115003783A (en) * | 2020-01-24 | 2022-09-02 | 伊特利姆再生公司 | Improvement of by-products of waste oil regeneration process |
| CN115003783B (en) * | 2020-01-24 | 2023-07-28 | 伊特利姆再生公司 | Improvement of by-product of waste oil regeneration process |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0745113A4 (en) | 1998-05-20 |
| RU2140433C1 (en) | 1999-10-27 |
| GB9408609D0 (en) | 1994-06-22 |
| EP0745113A1 (en) | 1996-12-04 |
| EG20462A (en) | 1999-05-31 |
| MX9603425A (en) | 1997-12-31 |
| CA2183433A1 (en) | 1995-08-17 |
| ZA951225B (en) | 1995-10-18 |
| AU700298B2 (en) | 1998-12-24 |
| WO1995021902A1 (en) | 1995-08-17 |
| TW265271B (en) | 1995-12-11 |
| JPH10500147A (en) | 1998-01-06 |
| AU1919195A (en) | 1995-08-29 |
| BR9506794A (en) | 1997-09-16 |
| CO4410379A1 (en) | 1997-01-09 |
| IL112623A (en) | 1999-03-12 |
| IL112623A0 (en) | 1995-05-26 |
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