CN104830515A - Method for regenerating waste lubricating oil - Google Patents
Method for regenerating waste lubricating oil Download PDFInfo
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- CN104830515A CN104830515A CN201510189002.4A CN201510189002A CN104830515A CN 104830515 A CN104830515 A CN 104830515A CN 201510189002 A CN201510189002 A CN 201510189002A CN 104830515 A CN104830515 A CN 104830515A
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Abstract
The invention provides a method for regenerating a waste lubricating oil. The method comprises the following steps: determining ideal components and non-ideal components in the waste lubricating oil; performing pretreatment and flash evaporation treatment on the waste lubricating oil so as to obtain a light oil and intermediate products; adding a selective catalyst to the intermediate products so as to enable the intermediate products to perform a selective catalytic reaction to strip off the non-ideal components in the intermediate products; refining the obtained distillate oil through a composite solvent, and then performing decompression and rectification treatment so as to obtain the light oil at the top of a tower and a regenerated basic oil which conforms to the standard of an API I type basic oil and has different stickiness levels. Through adoption of the method disclosed by the invention, the inherent quality of regenerated oil products is effectively improved, the product quality of the obtained regenerated oil achieves the standard of the API I type basic oil, and the comprehensive utilization ratio of the waste lubricating oil can reach more than 95%; direct waste water, direct waste liquid or direct water gas are not produced in the whole technology process, the method has the effects of environmental protection and energy conservation, and the industrialized production is facilitated.
Description
Technical field
The present invention relates to recycle recycling field and oil-refining chemical field, in particular to a kind of renovation process of waste lubricating oil.
Background technology
Along with the fast development of Chinese national economy, mechanical means, shipping vehicle and all trades and professions use the quantity of lubricating oil also in continuous increase.At present, China's lubricating oil year consumption more than 8,000,000 tons, and every year with 5% ~ 6% speed increase, within 2015, more than 1,000 ten thousand tons, the country that lubricating oil consumption is maximum in the world will be become.Meanwhile, China is also higher to the importation dependence of top-grade lubricating oil base oil at present, and within 2011, import lubricant base reaches 2,500,000 tons, and import Dependence rate reaches 25%, and China's Productions of middle and high grade lube oil base oil is in short supply.And the yield of China's waste lubricating oil is approximately about 4,000,000 tons every year at present, annual 6000000 tons ~ 8,000,000 tons after 2015, will be reached.Utilize if these waste lubricating oils obtain effective regeneration comprehensive, China's lubricant base situation in short supply will be alleviated to a certain extent, beneficial complement to Lube Oil Market, meeting the industry policy that national energy-saving reduces discharging recycling economy, is that china natural resources comprehensively recycles the embodiment with recycling economy development.
In addition, no matter waste lubricating oil is that burning, landfill all can to soil, water source environment generation severe contaminations or enter rivers etc.Owing to containing multiple toxicant in waste lubricating oil, if be poured into soil, can Plant death be caused, make microorganism extinction in contaminated soil; If enter drinking water source, 1 liter of waste lubricating oil will bring the pollution of 1,000,000 premium on currency, 1,000,000 premium on currency can reach 10 families other 1 year use water.Therefore, along with the mankind are to the raising day by day of environmental requirement, the regeneration of waste lubricating oil is also more and more subject to the attention of countries in the world.And in China, along with soil, water source environment pollute day by day serious, the pay attention to day by day of national living environment of surviving to ecological, environmental protective and the people, waste lubricant oil regeneration comprehensive utilization is also reduce the environmental pollution such as soil, water source, promotes the embodiment that national ecotope develops in a healthy way.
At present, waste lubricant oil regeneration comprehensive utilization market lacks the intervention of high-end technology, indigenous oil refining, little oil refining is prevailing, because of backward in technique, product yield is low, seriously polluted, bring resource again waste with secondary environmental pollution while, cause domestic oil product market confusion, false oil, slop oil flow into refined products market in a large number, bring severe compromise to all kinds of oil-using units.In recent years, country constantly put into effect the policy and the regulation that guide high-end technology to get involved waste lubricant oil regeneration market, supported and helped high-end technology to carry out waste oil regeneration project.
Therefore, high-quality waste lubricant oil regeneration utilizes the proposition of technology, for solution China lubrication oil circulation recycling, and the practical problemss such as energy scarcity, promote that national resources comprehensively recycles, develop a circular economy, form closed loop industrial chain, hit fake and forged oil product, oil purification market, reduce environmental pollution, promote Sustainable Development of Ecological Environment, there is important economic and social benefit.
But, the waste lubricant oil regeneration that Present Domestic extensively adopts utilizes technology substantially all also to rest on still distillation, atmospheric and vacuum distillation, molecule short-path distillation, the fractionation by distillation technology such as film evaporation technique, although these technology have certain industrialization effect, but these technology are all simplification technology, a set of perfect comprehensive recycling process program is not formed to the process of waste lubricating oil, it is lower that waste lubricating oil comprehensively recycles efficiency, usually 60% ~ 70% is only had, still there is the secondary wastes and pollution of resource, simultaneously, also there is technique instability to a certain extent in some technology, quality product is not easy to control, to waste lubricating oil raw material, there is the key technical problems such as selectivity not solve, therefore, these still can not as the comprehensive utilization technique leading Chinese waste lubricant oil regeneration to utilize market total health development.
The current regeneration for waste lubricating oil mainly contains the Technology of following several respects:
1, simple pre-treatment → atmospheric and vacuum distillation → acid-alkali refining (or clay-filtered);
2, flocculence removing impurities process → short-path distillation (molecular distillation) → clay-filtered;
3, pre-treatment → atmospheric and vacuum distillation → hydrofining.
And above-mentioned waste lubricant oil regeneration utilizes technology mainly to there is following shortcoming: the method adopting above-mentioned acid-alkali refining (or clay-filtered), or flocculence removing impurities process → short route distillation → clay-treated method, the generation of the environmental issue such as waste liquid, waste residue can be caused, and the treatment process imperfection of waste lubricating oil, operational condition are unstable, quality product is still weak, and does not reach concerned countries standard-required; Adopt pre-treatment → underpressure distillation → hydrorefined method, can not undesirable components fully in separating waste lubricating oil, especially can not effective removal heavy metal element, thus make hydrorefined processing condition limited, hydrogenation catalyst is poisoning, cannot carry out long-term suitability for industrialized production; And in the regeneration method of the above-mentioned waste lubricating oil provided, all clearly do not provide the regeneration comprehensive treatment process scheme of waste lubricating oil, the light Fuel obtained and mink cell focus process imperfection, do not reach concerned countries standard-required, make making a low multiple use of waste lubricating oil, generally only have 60% ~ 70%, fundamentally could not solve whole technical problems of waste lubricant oil regeneration comprehensive utilization, market adaptability is short of, and makes industrialization promotion limited.
Summary of the invention
The present invention is intended at least to solve one of technical problem existed in above-mentioned prior art.
For this reason, the object of the present invention is to provide a kind of renovation process of waste lubricating oil.The method is the solvent treatment type production technique of a kind of waste lubricating oil Comprehensive recycling, effectively can promote the interior quality of recovered oil product, and improve the comprehensive utilization ratio of waste lubricating oil, energy-conserving and environment-protective simultaneously, and is convenient to industrialization continuous seepage.
For achieving the above object, the invention provides a kind of renovation process of waste lubricating oil, it comprises the following steps:
Step S102: the physicochemical property and the composition that obtain pending waste lubricating oil, quantitatively determines the ideal composition in described waste lubricating oil and undesirable components;
Step S104: carry out pre-treatment to described waste lubricating oil, sloughs water wherein and/or mechanical impurity;
Step S106: carry out flash distillation process to pretreated waste lubricating oil, to slough water in waste lubricating oil and lighter hydrocarbons further, obtains lightweight oil and the first intermediate product;
Step S108: by described first intermediate product and WO
3, NiO, activated alumina and thanomin mixing solutions mixing, make the first intermediate product generation selective catalysis reaction after adding described mixing solutions, to slough the undesirable components in described first intermediate product, obtain the second intermediate product, be separated and obtain distillate and subtract end oil;
Step S110: to the mixed solvent of described distillate cloth mercaptan and N-Methyl pyrrolidone by volume the agent-oil ratio (i.e. the volume ratio of described mixed solvent and described distillate) of 1:4 ~ 1:6 carry out double solvents and refine, obtain intermediates (the various metal element contents of these intermediates are less than 2 μ g/g respectively);
Step S112: carry out rectification under vacuum process to described intermediates, and carry out cut cutting, obtains overhead light oil and meets the Reclaimed Base Oil of different viscosity rank of API (American Petroleum Institute (API)) I class base oil standard.
In the solvent treatment type production technique that above-mentioned waste lubricating oil provided by the invention comprehensively recycles, first the physicochemical property, the composition that obtain pending waste lubricating oil is needed, to determine ideal composition in waste lubricating oil and undesirable components, be convenient to follow-up formulation processing condition, to protect the ideal composition in waste lubricating oil, remove and transform the undesirable components in waste lubricating oil; Then carry out pre-treatment and flash distillation process to waste lubricating oil, pre-treatment is to slough water in waste lubricating oil and/or mechanical impurity; Flash distillation process, further to dewater to waste lubricating oil and to take off gently, obtains lightweight oil and the first intermediate product; Then to bringing Selection In property catalyzer in the first intermediate product, the first intermediate product generation selective catalysis reaction is made, to slough the undesirable components in the first intermediate product, as undesirable components such as metallic compound, nonmetallic compound and metallic impurity; Then the distillate obtained the undesirable components of sloughing in the first intermediate product carries out double solvents and refines, and obtains intermediates; Rectification under vacuum process is carried out to intermediates, cut is cut, obtain overhead light oil and the Reclaimed Base Oil meeting the different viscosity rank that API I class base oil standard requires.
In the renovation process of above-mentioned waste lubricating oil of the present invention, it should be noted that, in described step S102, the method of the physicochemical property and composition that obtain pending waste lubricating oil is ordinary skill in the art means, ideal composition in described waste lubricating oil and undesirable components are also that those skilled in the art just can distinguish according to general knowledge known in this field, and these repeat no more in this article.
In the renovation process of above-mentioned waste lubricating oil, preferably, in described step S108, WO
3, NiO, activated alumina and thanomin mixing solutions in, WO
3, NiO, activated alumina and thanomin mass ratio be 1:1:2:200 ~ 1:1:2:300; And the mass ratio 1:400 ~ 1:600 of thanomin and described intermediate product.
In the renovation process of above-mentioned waste lubricating oil, preferably, in described step S108, the condition of described selective catalysis reaction is: 220 DEG C ~ 320 DEG C, carry out selective catalysis under condition of normal pressure and react 2 hours ~ 4 hours.
In the renovation process of above-mentioned waste lubricating oil, preferably, in described step S108, can, under the pressure of 5 ~ 10Pa, the mode of vacuum extraction be adopted to isolate distillate and subtract end oil.
According to the specific embodiment of the present invention, preferably, in the renovation process of above-mentioned waste lubricating oil, in described step S108, the content of the various metallic elements in described second intermediate product is less than 2 μ g/g respectively.Owing to there is metallic compound in waste lubricating oil, the undesirable components such as nonmetallic compound and metallic impurity, if the undesirable components in waste lubricating oil is separated not thorough, directly can affect end product quality, do not reach relevant criterion requirement, and after selective catalysis reaction, the undesirable components in the first intermediate product can be sloughed, as metallic compound, the undesirable components such as nonmetallic compound and metallic impurity, the technical indicator of the stock oil after process is made to reach Ca, Ba, Zn, Mg, Mo, Fe, Cu, Al, Cr, lower than 2 μ g/g, (ppm refers to hundred content very much to the metal element contents such as Sn, 2ppm refers to 2/1000000ths), the final recovered oil quality product after rectification under vacuum process is made to reach API I class base oil standard.It should be noted that, the selective catalysis reaction of the first intermediate product can be carried out in the thin-film evaporator of routine.
According to the specific embodiment of the present invention, preferably, in the renovation process of above-mentioned waste lubricating oil, in described step S112, under the condition of the pressure of 5 ~ 50Pa, three grades of vacuum extraction, rectification under vacuum process is carried out to described intermediates, and carrying out cut cutting, the different lateral line dischargings of acquisition comprise the API I class base oil of light Fuel and different viscosity grade.More preferably, the temperature range of carrying out cut cutting is respectively a temperature in 200 ± 5 DEG C, 280 ± 5 DEG C, 320 ± 5 DEG C, 350 ± 5 DEG C or several temperature.It should be noted that, described rectification under vacuum process is carried out in vacuum rectification tower.The concrete technology parameter of described vacuum rectification tower, such as reflux ratio and theoretical plate number etc., can by the adjustment of on an equal basis not carrying out routine of those skilled in the art according to material inlet.
According to the specific embodiment of the present invention, preferably, in the renovation process of above-mentioned waste lubricating oil, in described step S104, described pre-treatment comprises: the mode (more preferably, the time of repose of sedimentation is not less than 24 hours) described waste lubricating oil being adopted to 50 DEG C ~ 70 DEG C of preheating sedimentations, and/or the mode adopting hydrophobic membrane to filter, to slough the materials such as water in waste lubricating oil and mechanical impurity, this treatment process is simple to operate, is easy to realize.
According to the specific embodiment of the present invention, preferably, in the renovation process of above-mentioned waste lubricating oil, in described step S106, described flash distillation process is at normal pressure, and temperature is carry out under the condition of 120 DEG C ~ 200 DEG C.This flash distillation process can adopt flashing tower to carry out.
According to the specific embodiment of the present invention, preferably, in the renovation process of above-mentioned waste lubricating oil, in described step S110, in described mixed solvent, the volume ratio of cloth mercaptan and N-Methyl pyrrolidone is 1:1.5 ~ 1:2.5.
According to the specific embodiment of the present invention, preferably, in the renovation process of above-mentioned waste lubricating oil, described step S110 completes in solvent tower, and operational condition is normal pressure, temperature 70 C ~ 120 DEG C.
According to the specific embodiment of the present invention, preferably, comprise step S114 at the renovation process of above-mentioned waste lubricating oil: subtract end oil described in described step S108 process is obtained and carry out double solvents extracting, obtain heavy basestock; And/or subtract end oil described in described step S108 process obtained and carry out thermo-cracking, obtain lightweight oil and residual oil; And/or subtract end oil described in described step S108 process obtained and carry out carbon black process, obtain carbon black; And/or subtract end oil described in described step S108 process being obtained and be processed into bituminous matter and/or refinery coke.Wherein, described thermo-cracking can complete in pyrolyzer, and the operational condition of thermo-cracking can be normal pressure, temperature 350 DEG C ~ 420 DEG C.Described carbon black process can complete in black reactor, and concrete technology condition can be preheated to 160 DEG C ~ 200 DEG C for subtracting end oil, mixes with the hot combustion gas stream of 1600 DEG C ~ 2100 DEG C, and cracking obtains carbon black.Described be processed into bitum processing condition can in process furnace 180 DEG C ~ 220 DEG C process complete.The described processing condition being processed into refinery coke can be that 300 DEG C ~ 350 DEG C process complete in process furnace.
According to the specific embodiment of the present invention, preferably, in the renovation process of above-mentioned waste lubricating oil, in described step S114, described double solvents comprises the propane and pentane that volume ratio is 1:1.5 ~ 1:3, the working temperature of described double solvents extracting is 90 DEG C ~ 120 DEG C, and operating pressure is 2MPa ~ 4MPa.This double solvents extraction procedure subtracting end oil is simple, and this step can complete in solvent tower.
According to the specific embodiment of the present invention, preferably, in the renovation process of above-mentioned waste lubricating oil, described step S114 comprises further: carry out carbon black process to the residual oil that described thermo-cracking obtains, and obtains carbon black; And/or the Residual cracking that described thermo-cracking obtains is become bituminous matter and/or refinery coke.Here carbon black treatment condition and work become the treatment condition of bituminous matter and/or refinery coke identical with the corresponding conditions mentioned herein-above set forth.
According to the specific embodiment of the present invention, preferably, also step S116 is comprised: under the condition of normal temperature and pressure at the renovation process of above-mentioned waste lubricating oil, the process of electrochemistry etherificate is carried out to the described lightweight oil that described step S106 and/or described step S114 process obtain, obtains clean light Fuel.More preferably, the step of described electrochemistry etherificate process is: by described lightweight oil and catalyzer 1:(0.1 ~ 0.5 by volume) fully contact mixing after 10 ~ 30 minutes, be 1200m in hertzian wave wave-number range
-1~ 1800m
-1electromagnetic wave environment under, electrochemistry etherification reaction occurs, and the reaction times is 20 ~ 50 minutes.Used catalyst is alcohol compound, is preferably methyl alcohol.The equipment that the process of electrochemistry etherificate adopts can be the electrochemistry etherificate equipment of this area routine, the electrochemical instrument that such as can generate electromagnetic waves.More specifically, electrochemistry etherificate equipment as shown in Figure 3 can be adopted, this equipment comprises: reactor 1, first electrode 2, second electrode 3, electromagnetic wave generating device 4, described first electrode 2 is connected with described electromagnetic wave generating device 4 with the second electrode 3, and insert in described reactor 1, the top of described reactor 1 is provided with opening for feed 5, bottom is provided with discharge port 6.Wherein, described reactor 1 can be steel reactor, and can top cover be provided with, described first electrode 2 and the second electrode 3 can be fixed on this top cover, do not touch with the bottom connection of described reactor 1, and described first electrode 2 and the second electrode 3 can be copper electrode plate, and described electromagnetic wave generating device 4 can be the electromagnetic wave generator of this area routine.The title of described first electrode 2 and the second electrode 3 is only for making statement more clear, and " first " and " second " is wherein without substantive difference.When carrying out electrochemistry etherification reaction, material enters from the opening for feed 5 at reactor 1 top, until flooded by the first electrode 2, second electrode 3, after making lightweight oil fully contact mixing with catalyzer, opens electromagnetic wave generating device 4, at 1200m
-1~ 1800m
-1wave-number range in (voltage can be 220V), electrochemistry etherification reaction occurs, and react after terminating, product is released from the discharge port 6 bottom reactor 1.The process of electrochemistry etherificate is carried out to lightweight oil, adopt the method for electrochemistry etherificate process, make the olefin saturated in lightweight oil, improve stability and the combustionproperty of light Fuel product, improve the quality of light Fuel, light Fuel quality product is up to state standards requirement.The renovation process of above-mentioned waste lubricating oil provided by the invention, compared with traditional waste lubricant oil regeneration treatment technology, the ideal composition in waste lubricating oil can be made full use of, remove or transform the undesirable components in waste lubricating oil, and adopt double solvents refinement treatment, the interior quality of remarkable lifting recovered oil product, the recovered oil quality product of acquisition reaches API I class base oil standard; Carry out the production of multivariant solvent extraction, production of carbon black, refinery coke and bituminous matter to subtracting end oil simultaneously, and the process of electrochemistry etherificate is carried out to lightweight oil, improve light Fuel stability, produce the comprehensive recycling of clean light Fuel etc., the comprehensive utilization ratio of waste lubricating oil is significantly improved, bring up to more than 95% from 60% ~ 70%, adequately achieve the Comprehensive recycling of waste lubricating oil.
Moreover, in the bulk treatment process of the renovation process of above-mentioned waste lubricating oil provided by the invention, produce without direct waste water, waste liquid, the waste gas three wastes, effectively can reduce the quantity producing waste liquid, residue, environmental pollution is little, available protecting environment, and this treating processes carried out energy-saving design, make that the heat and the gas that produce are capable of circulation uses by oneself, reach good environmental protection and energy-saving effect; And take overall industrial equipment function modoularization; conventional thin-film evaporator; the technology such as the plurality of devices Integration Designs such as Conventional electrochemical etherificate equipment and vacuum rectification tower, DCS distribute control strategy; realize the Automated condtrol produced and the security guaranteeing production; this technology is made to have stronger reproducibility; the mass-producing being beneficial to different geographical is founded the factory, and is convenient to the suitability for industrialized production realizing waste lubricating oil.
Accompanying drawing explanation
Fig. 1 is the flow chart of steps of the renovation process of waste lubricating oil in the embodiment of the invention.
Fig. 2 is the process flow sheet of the renovation process of waste lubricating oil in the embodiment of the invention.
Fig. 3 is the structural representation of the electrochemistry etherificate equipment in the embodiment of the invention.
Primary clustering nomenclature:
Reactor 1, first electrode 2, second electrode 3, electromagnetic wave generating device 4, opening for feed 5, discharge port 6.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
It should be noted that, when not conflicting, the feature in the embodiment of the application and embodiment can combine mutually.
Describe in detail further below in conjunction with Fig. 1, Fig. 2 and the renovation process of following examples to waste lubricating oil of the present invention.
As depicted in figs. 1 and 2, the renovation process of waste lubricating oil provided by the invention can comprise the following steps:
Step S102: the physicochemical property and the composition that obtain pending waste lubricating oil, quantitatively determines the ideal composition in described waste lubricating oil and undesirable components;
Step S104: then make described waste lubricating oil enter slurry tank, 50 DEG C ~ 70 DEG C preheating sedimentations are adopted to described waste lubricating oil and/or adopts hydrophobic membrane to filter, slough the material such as water and mechanical impurity in waste lubricating oil, obtain pretreated waste lubricating oil, this treatment process is simple to operate, is convenient to processing;
Step S106: carry out flash distillation process to described pretreated waste lubricating oil in flashing tower, dewaters and de-lighter hydrocarbons further, obtains lightweight oil and the first intermediate product;
Step S108: by described first intermediate product and WO
3, NiO, activated alumina and thanomin mixing solutions mixing, make the first intermediate product after adding described mixing solutions, at 220 DEG C ~ 320 DEG C, selective catalysis reaction occur, to slough the undesirable components in described first intermediate product, obtain the second intermediate product, be separated and obtain distillate and subtract end oil, ensure that the content of metallic element Ca, Ba, Zn, Mg, Mo, Fe, Cu, Al, Cr, the Sn etc. in the undesirable components in the second intermediate product obtained is less than 2 μ g/g respectively;
Step S110: the described distillate sloughing undesirable components is sent into solvent treatment tower, with cloth mercaptan and N-Methyl pyrrolidone mixed solvent, the agent-oil ratio of 1:4 ~ 1:6 carries out deep refining by volume, the element such as further decolouring, de-taste, de-S, N, P, obtain intermediates, and the extraction oil in solvent refining processes is reclaimed respectively with raffinating oil, and recycle;
Step S112: described intermediates are sent into vacuum rectification tower, under the condition of the pressure of 5 ~ 50Pa, three grades of vacuum extraction, underpressure distillation and cut cutting are carried out to described intermediates, obtain the Reclaimed Base Oil meeting API I class base oil standard of overhead light oil and different viscosity rank;
Step S114: subtract end oil described in described step S108 process is obtained and carry out double solvents extracting, obtain heavy basestock, described double solvents comprises the propane and pentane that volume ratio is 1:1.5 ~ 1:3, the working temperature of described double solvents extracting is 90 DEG C ~ 120 DEG C, operating pressure is 2MPa ~ 4MPa, and this double solvents extraction procedure subtracting end oil is simple; And/or subtract end oil described in described step S108 process obtained and carry out thermo-cracking, obtain lightweight oil and residual oil; And/or subtract end oil described in described step S108 process obtained and carry out carbon black process, obtain carbon black; And/or subtract end oil described in described step S108 process being obtained and be processed into bituminous matter and/or refinery coke; Carbon black process is carried out to the residual oil that described thermo-cracking obtains, obtains carbon black; And/or the Residual cracking that described thermo-cracking obtains is become bituminous matter and/or refinery coke;
Step S116: under the condition of normal temperature and pressure, the process of electrochemistry etherificate is carried out to the described lightweight oil that described step S106 and/or described step S114 process obtain, the step of described electrochemistry etherificate process is: by described lightweight oil and catalyzer 1:(0.1 ~ 0.5 by volume) fully contact mixing after 10 ~ 30 minutes, be 1200m in hertzian wave wave-number range
-1~ 1800m
-1electromagnetic wave environment under, electrochemistry etherification reaction occurs, and the reaction times is 20 ~ 50 minutes, obtains clean light Fuel.
Embodiment 1
1# waste lubricating oil shown in his-and-hers watches 1 carries out regeneration according to above-mentioned technique and refines.
One, 1# waste lubricating oil composition
Table 1
Two, solvent treatment regenerative process
First by 1# waste lubricating oil in slurry tank, sedimentation 24h at 60 DEG C of temperature, squeezes in flashing tower afterwards, flash distillation process at normal pressure 180 DEG C, distills out the light hydrocarbon component of mass percent 2% and the moisture of 0.54%, then squeezes in thin-film evaporator by remaining ingredient, with WO
3, NiO, activated alumina and thanomin mixing solutions mixing, WO
3, NiO, activated alumina and thanomin mass ratio be 1:1:2:200; And the mass ratio 1:500 of thanomin and described remaining ingredient, 280 DEG C, carry out selective catalysis under condition of normal pressure and react 2 hours ~ 4 hours, then, under 5Pa pressure, mass percent 82.9% distillate is isolated and mass percent 14.56% subtracts end oil for 280 DEG C.82.9% distillate is sent into solvent treatment tower, with cloth mercaptan and N-Methyl pyrrolidone by volume 1:2 be mixed into mixing solutions, the agent-oil ratio of 1:4 carries out deep refining to said components under normal pressure, temperature 70 C by volume, extract oil out and send into vacuum still, raffinating oil to reclaim in solvent recovery tower enters solvent treatment tower again; Above-mentioned material in vacuum still with 5Pa pressure, respectively at 280 DEG C, 320 DEG C, 350 DEG C of base oils obtaining different viscosity grades.The end oil that subtracts of 14.56% is sent in cleavage column, at normal pressure, at 420 DEG C, cracking generates the lightweight oil of 12.7% and the furnace bottom residual oil of 1.86%, 2% light hydrocarbon component obtained after this 12.7% lightweight oil and flash distillation process is mixed and together carries out etherificate process through electrochemistry etherificate equipment as shown in Figure 3 (this equipment comprises: reactor 1, first electrode 2, second electrode 3, electromagnetic wave generating device 4, described first electrode 2 is connected with described electromagnetic wave generating device 4 with the second electrode 3, and insert in described reactor 1, the top of described reactor 1 is provided with opening for feed 5, bottom is provided with discharge port 6, wherein, described reactor 1 can be steel reactor, and can top cover be provided with, described first electrode 2 and the second electrode 3 can be fixed on this top cover, do not touch with the bottom connection of described reactor 1, and described first electrode 2 and the second electrode 3 can be copper electrode plate, and described electromagnetic wave generating device 4 can be the electromagnetic wave generator of this area routine, the title of described first electrode 2 and the second electrode 3 is only for making statement more clear, and " first " and " second " is wherein without substantive difference, when carrying out electrochemistry etherification reaction, material enters from the opening for feed 5 at reactor 1 top, until the first electrode 2, second electrode 3 is flooded, after reaction terminates, product is released from the discharge port 6 bottom reactor 1), the step of described electrochemistry etherificate process is: under the condition of normal temperature, normal pressure, described lightweight oil (i.e. 12.7% lightweight oil and 2% light hydrocarbon component sum) and catalyzer are injected in the reactor 1 of electrochemistry etherificate equipment according to the volume ratio of 1:0.2, abundant contact mixing 15 minutes, then electromagnetic wave generating device 4 is opened, at 1200m
-1~ 1800m
-1wave-number range in (voltage can be 220V), electrochemistry etherification reaction occurs, and the reaction times is 20 minutes, and catalyzer used is methyl alcohol, the clean gasoline of acquisition good security, the furnace bottom residual oil of residue 1.86%, sends into calcining furnace 320 DEG C calcining and generates petroleum coke.Three, regeneration comprehensive utilization ratio
Table 2
Four, Quality of Reclaimed Base Oil detects data
Table 3
Embodiment 2
Waste lubricating oil shown in his-and-hers watches 4 carries out regeneration according to above-mentioned technique and refines.
One, 2# waste lubricating oil composition
Table 4
Two, solvent treatment regenerative process
First by 2# waste lubricating oil in slurry tank, sedimentation 24h at 60 DEG C of temperature, squeezes in flashing tower afterwards, normal pressure, flash distillation process at 200 DEG C, distill out the light hydrocarbon component of mass percent 1% and the moisture of 0.24%, then remaining ingredient is squeezed in thin-film evaporator, with WO
3, NiO, activated alumina and thanomin mixing solutions mixing, WO
3, NiO, activated alumina and thanomin mass ratio be 1:1:2:200; And the mass ratio 1:500 of thanomin and described remaining ingredient, 280 DEG C, carry out selective catalysis under condition of normal pressure and react 2 hours ~ 4 hours, then, under 5Pa pressure, mass percent 87.6% distillate is isolated and mass percent 11.16% subtracts end oil for 280 DEG C.87.6% distillate is sent into solvent treatment tower, with cloth mercaptan and N-Methyl pyrrolidone by volume 1:2 be mixed into mixing solutions, the agent-oil ratio of 1:5 carries out deep refining to said components at normal pressure, temperature 75 DEG C by volume, extract oil out and send into vacuum still, raffinating oil to reclaim in solvent recovery tower enters solvent treatment tower again; Above-mentioned material in vacuum still with 5Pa pressure, respectively at 280 DEG C, 320 DEG C, 350 DEG C of base oils obtaining different viscosity grades.The end oil that subtracts of 11.16% is sent in cleavage column, at normal pressure, at 420 DEG C, cracking generates the lightweight oil of 9.14% and the furnace bottom residual oil of 2.02%, 1% light hydrocarbon component obtained after this 9.14% lightweight oil and flash distillation process is mixed and together carries out etherificate process through electrochemistry etherificate equipment as shown in Figure 3, the step of described electrochemistry etherificate process is: at normal temperature, under the condition of normal pressure, described lightweight oil (i.e. 9.14% lightweight oil and 1% light hydrocarbon component sum) and catalyzer are injected in the reactor 1 of electrochemistry etherificate equipment according to the volume ratio of 1:0.25, abundant contact mixing 15 minutes, then electromagnetic wave generating device 4 is opened, at 1200m
-1~ 1800m
-1wave-number range in (voltage can be 220V), electrochemistry etherification reaction occurs, and the reaction times is 25 minutes, and catalyzer used is methyl alcohol, the clean gasoline of acquisition good security, the furnace bottom residual oil of residue 2.02%, sends into calcining furnace 320 DEG C calcining and generates petroleum coke.
Three, regeneration comprehensive utilization ratio
Table 5
| Sample ID | Base oil fractions | Etherificate clean gasoline | Petroleum coke | Total recovery |
| Yield | Yield | |||
| 2# waste lubricating oil | 87.6％ | 10.14％ | 2.02％ | 99.76％ |
Four, Quality of Reclaimed Base Oil detects data
Table 6
Embodiment 3
3# waste lubricating oil shown in his-and-hers watches 7 carries out regeneration according to above-mentioned technique and refines.
One, 3# waste lubricating oil composition
Table 7
Two, solvent treatment regenerative process
First by 3# waste lubricating oil in slurry tank, sedimentation 24h at 70 DEG C of temperature, squeezes in flashing tower afterwards, normal pressure, flash distillation process at 200 DEG C, distill out the light hydrocarbon component of mass percent 3% and the moisture of 2.54%, then remaining ingredient is squeezed in thin-film evaporator, with WO
3, NiO, activated alumina and thanomin mixing solutions mixing, WO
3, NiO, activated alumina and thanomin mass ratio be 1:1:2:200; And the mass ratio 1:500 of thanomin and described remaining ingredient, 280 DEG C, carry out selective catalysis under condition of normal pressure and react 2 hours ~ 4 hours, then, under 5Pa pressure, mass percent 84.8% distillate is isolated and mass percent 9.66% subtracts end oil for 280 DEG C.84.8% distillate is sent into solvent treatment tower, with cloth mercaptan and N-Methyl pyrrolidone by volume 1:2 be mixed into mixing solutions, the agent-oil ratio of 1:5 carries out deep refining to said components at normal pressure, temperature 75 DEG C by volume, extract oil out and send into vacuum still, raffinating oil to reclaim in solvent recovery tower enters solvent treatment tower again; Above-mentioned material in vacuum still with 5Pa pressure, respectively at 280 DEG C, 320 DEG C, 350 DEG C of base oils obtaining different viscosity grades.The end oil that subtracts of 9.66% is sent in cleavage column, at normal pressure 420 DEG C, cracking generates the lightweight oil of 6.28% and the furnace bottom residual oil of 3.38%, 3% light hydrocarbon component obtained after this 6.28% lightweight oil and flash distillation process is mixed and together carries out etherificate process through electrochemistry etherificate equipment as shown in Figure 3, the step of described electrochemistry etherificate process is: at normal temperature, under the condition of normal pressure, be be injected in the reactor 1 of electrochemistry etherificate equipment by described lightweight oil (i.e. 6.28% lightweight oil and 3% light hydrocarbon component sum) and catalyzer according to the volume ratio of 1:0.2, abundant contact mixing 15 minutes, then electromagnetic wave generating device 4 is opened, at 1200m
-1~ 1800m
-1wave-number range in (voltage can be 220V), electrochemistry etherification reaction occurs, and the reaction times is 25 minutes, and catalyzer used is methyl alcohol, the clean gasoline of acquisition good security, the furnace bottom residual oil of residue 3.38%, sends into calcining furnace 320 DEG C calcining and generates petroleum coke.
Three, regeneration comprehensive utilization ratio
Table 8
Four, Quality of Reclaimed Base Oil detects data
Table 9
Can be found out by above embodiment, the renovation process of waste lubricating oil provided by the invention can reach following beneficial effect:
(1) to originate changeable feature according to waste lubricating oil, Comprehensive evaluation is carried out to waste lubricating oil, propose Comprehensive recycling scheme, realize, to waste lubricating oil " eat dry squeeze clean ", making waste lubricating oil comprehensive utilization ratio reach more than 95%;
(2) on the basis of waste lubricating oil comprehensive evaluation, adopt thin-film evaporator to remove and transform the undesirable components in waste lubricating oil, adopt double solvents refinement treatment, significantly promote the interior quality of recovered oil product, the recovered oil quality product of acquisition reaches API I class base oil standard;
(3) process of electrochemistry etherificate is adopted to lightweight oil, make the olefin saturated in lightweight oil, the requirement and the unsaturated hydrocarbons content in lightweight oil is up to state standards, obtain clean light Fuel;
(4) in the whole production process of waste lubricating oil process, produce without direct waste water, waste liquid, the waste gas three wastes, available protecting environment; The whole technological process of production carries out energy-saving design, make the heat of generation and gas capable of circulation personal, reach the not only energy-conservation but also effect of environmental protection;
(5) technology such as plurality of devices Integration Design, DCS distribute control strategy such as overall industrial equipment function modoularization, conventional thin-film evaporator, Conventional electrochemical etherificate equipment and vacuum still are taked, realize the Automated condtrol produced and the security guaranteeing production, make the treatment technology of this waste lubricating oil have stronger reproducibility, be convenient to suitability for industrialized production.
In sum, the production technique of solvent treatment type waste lubricating oil Comprehensive recycling provided by the invention, by carrying out selective catalysis process to the intermediate product of waste lubricating oil after pre-treatment and flash distillation, the ideal composition in waste lubricating oil can be made full use of, slough the undesirable components in waste lubricating oil, and adopt that double solvents is refining to be further processed, effectively improve the inner quality of recovered oil product, after rectification under vacuum, obtain the Reclaimed Base Oil meeting API I class base oil standard of different viscosity grade; And the process of electrochemistry etherificate is carried out to the lightweight oil obtained in waste lubricating oil treating processes, obtain and there is good stability and combustible light Fuel; Moreover, the production technology of this solvent treatment type waste lubricating oil Comprehensive recycling to be originated changeable feature according to waste lubricating oil, Comprehensive recycling can be carried out to waste lubricating oil, the waste lubricating oil achieving whole process " eats dry squeezing only ", makes waste lubricating oil comprehensive utilization ratio reach more than 95%; And whole production process, produce without direct waste water, waste liquid, waste gas, there is environmental protection, energy-conservation effect, be convenient to suitability for industrialized production.
Claims (9)
1. a renovation process for waste lubricating oil, it comprises the following steps:
Step S102: the physicochemical property and the composition that obtain pending waste lubricating oil, quantitatively determines the ideal composition in described waste lubricating oil and undesirable components;
Step S104: carry out pre-treatment to described waste lubricating oil, sloughs water wherein and/or mechanical impurity;
Step S106: carry out flash distillation process to pretreated waste lubricating oil, to slough water in waste lubricating oil and lighter hydrocarbons further, obtains lightweight oil and the first intermediate product;
Step S108: by described first intermediate product and WO
3, NiO, activated alumina and thanomin mixing solutions mixing, make the first intermediate product generation selective catalysis reaction after adding described mixing solutions, to slough the undesirable components in described first intermediate product, obtain the second intermediate product, be separated and obtain distillate and subtract end oil;
Step S110: to the mixed solvent of described distillate cloth mercaptan and N-Methyl pyrrolidone by volume the agent-oil ratio of 1:4 ~ 1:6 carry out double solvents and refine, obtain intermediates;
Step S112: carry out rectification under vacuum process to described intermediates, and carry out cut cutting, obtains overhead light oil and meets the Reclaimed Base Oil of different viscosity rank of API I class base oil standard.
2. renovation process according to claim 1, wherein, in described step S108, the content of the various metallic elements in described second intermediate product is less than 2 μ g/g respectively.
3. renovation process according to claim 1, wherein, in described step S112, carries out rectification under vacuum process to described intermediates, and carries out cut cutting under the condition of the pressure of 5 ~ 50Pa, three grades of vacuum extraction.
4. renovation process according to claim 1, wherein, in described step S104, described pre-treatment comprises: adopt 50 DEG C ~ 70 DEG C preheating sedimentations to described waste lubricating oil and/or adopt hydrophobic membrane to filter.
5. the renovation process according to any one of claim 1-4, it also comprises step S114: subtract end oil described in obtaining described step S108 process and carry out double solvents extracting, obtains heavy basestock; And/or subtract end oil described in described step S108 process obtained and carry out thermo-cracking, obtain lightweight oil and residual oil; And/or subtract end oil described in described step S108 process obtained and carry out carbon black process, obtain carbon black; And/or subtract end oil described in described step S108 process being obtained and be processed into bituminous matter and/or refinery coke.
6. renovation process according to claim 5, wherein, described step S114 comprises further: carry out carbon black process to the residual oil that described thermo-cracking obtains, and obtains carbon black; And/or the Residual cracking that described thermo-cracking obtains is become bituminous matter and/or refinery coke.
7. renovation process according to claim 5, wherein, in described step S114, described double solvents comprises the propane and pentane that volume ratio is 1:1.5 ~ 1:3, the working temperature of described double solvents extracting is 90 DEG C ~ 120 DEG C, and operating pressure is 2MPa ~ 4MPa.
8. renovation process according to claim 1 or 5, it also comprises step S116: under the condition of normal temperature and pressure, carries out the process of electrochemistry etherificate to the described lightweight oil that described step S106 and/or described step S114 process obtain, and obtains clean light Fuel.
9. renovation process according to claim 8, wherein, in described step S116, the step of described electrochemistry etherificate process is: by described lightweight oil and catalyzer 1:(0.1 ~ 0.5 by volume) fully contact mixing after 10 ~ 30 minutes, be 1200m in hertzian wave wave-number range
-1~ 1800m
-1electromagnetic wave environment under, electrochemistry etherification reaction occurs, and the reaction times is 20 ~ 50 minutes.
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