CN106906040A - A kind of renovation process of waste lubricating oil - Google Patents
A kind of renovation process of waste lubricating oil Download PDFInfo
- Publication number
- CN106906040A CN106906040A CN201710116537.8A CN201710116537A CN106906040A CN 106906040 A CN106906040 A CN 106906040A CN 201710116537 A CN201710116537 A CN 201710116537A CN 106906040 A CN106906040 A CN 106906040A
- Authority
- CN
- China
- Prior art keywords
- lubricating oil
- waste lubricating
- oil
- renovation process
- adsorbent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C10M175/0008—Working-up used lubricants to recover useful products ; Cleaning with the use of adsorbentia
-
- 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
- C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
-
- 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
- C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
- C10M175/0033—Working-up used lubricants to recover useful products ; Cleaning by thermal processes using distillation processes; devices therefor
-
- 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
- C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
- C10M175/0041—Working-up used lubricants to recover useful products ; Cleaning by thermal processes by hydrogenation processes
-
- 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
- C10M175/0058—Working-up used lubricants to recover useful products ; Cleaning by filtration and centrifugation processes; apparatus therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a kind of renovation process of waste lubricating oil, waste lubricating oil is dehydrated, makes water content<Filtered after 0.5wt%, primary adsorption is first carried out after filtering, secondary absorption is carried out again, its content of beary metal is set to be less than 6 μ g/g, then hydrogenation reaction is carried out to waste lubricating oil, reclaimed oil is obtained, the reclaimed oil is fractionated, and can obtain low-sulphur oil, low-sulfur diesel fraction and lube base oil；Wherein, the adsorbent of primary adsorption is alumina adsorbant；The adsorbent of secondary absorption is chitosan derivatives modified adsorbent.The present invention can effectively remove the various undesirable components in waste lubricating oil, obtain reclaimed lubricating oil base oil and fuel oil ingredient best in quality.The characteristics of adsorbent of the invention has good stability, activity high, long lifespan, regenerative process does not result in environmental pollution, and rational process route and condition are selected in addition.
Description
Technical field
The present invention relates to technical field of petrochemical industry, in particular to a kind of renovation process of waste lubricating oil.
Background technology
In recent years, with the rapid growth of China's automobile market recoverable amount, the consumption of lubricating oil increases year by year.At present I
State's lubricating oil usage amount is up to 7,600,000 tons/year, and every annual meeting is with 24% speed increase, and waste lubricating oil discharge capacity is high
Up to more than 500 ten thousand tons/it is annual, it is contemplated that to the year two thousand twenty, the demand for lubricating oil of Chinese market will be doubled, and China will also eventually become
The generation big country of the first waste lubricating oil in the world.Lubricating oil due to being polluted by the external world, is produced substantial amounts of in the course of the work
Colloid, oxide so as to reduce so that friction out of hand, reduce abrasion, cool the effects such as, but its main component do not have
Change, if abandoning or burning waste oil, not only cause the significant wastage of the energy, and serious environmental pollution can be caused.
With the increasingly depleted of petroleum resources, the enhancing of people's environmental consciousness and rising steadily for oil price, waste lubricating oil are made profits again
With the great attention for receiving countries in the world.
The impurity contained in waste lubricating oil typically mainly has：Moisture, the impurity (gold that such as dust, asphalitine, abrasion are got off
Category), light component (petrol and diesel oil, the lubricating oil chain rupture product that are mixed into), lube oil additive and catabolite, the rotten component in part
(unsaturated hydrocarbons, the alcohols and acids of oxidation generation that are produced such as the chain rupture of lubrication oil molecule).Most hydro carbons in waste lubricating oil
(about 90%) does not have rotten, can recycle.By removing impurity and by rotten component by proper treatment, can give up
Lubricant oil regeneration is utilized, it might even be possible to be regenerated as high-quality lube base oil.Therefore waste lubricant oil regeneration is reclaimed and not only may be used
With environmental protection and resource recycling can be realized, with good social and economic benefit.
With the continuous improvement of quality of lubrication oil specification and standard, the species and consumption of additive also constantly exist in lubricating oil
Increase, increased the difficulty of reclaiming waste lubricating oil technique；Simultaneously with increasingly strict, the waste oil regeneration technology of environmental regulation
The middle technology for producing secondary pollution will gradually be eliminated, conventional technology such as acid-clay-filtered type waste lubricating oil recovery process,
A large amount of acid, spent bleaching clay and waste water can be produced during recovery, and the product quality that the technique is provided is also very poor, does not reach existing
The standard of row lube base oil, these situations all promote the appearance of more advanced waste oil technique.Waste oil hydrofining technology because
Its feature of environmental protection higher, economy and operability, are more and more paid attention to, have become replacement acid-it is clay-filtered,
The new technology of solvent extraction process.
The patent of Publication No. CN1132922C discloses a kind of combined technique for reclaiming waste lubricating oil, and the method is adopted
Suspension bed hydrogenation process process is used, waste oil is carried out at hydrogenation as catalyst using the metal fillings and compound of waste oil Crude Oil
Reason, then through simple filtration, distillation, fixed bed hydrogenation be refined, the separation of light component product, you can obtain Reclaimed Base Oil and by-product
Product light oil.The shortcoming of the method is that the metallic compound in waste oil is mainly the decomposition of the lube oil additives such as calcium, magnesium, zinc
Product, these metallic compounds to hydrogenation reaction substantially without catalytic action, so the hydrogenation process can not effectively take off
Except hetero atoms such as S, N, the O in waste oil.
Application No. CN200710098992.6 discloses a kind of waste lubricating oil hydrogenation reproducing method.The method be mainly by
Raw material waste lubricating oil is dehydrated, is filtered and adsorption treatment, removes moisture therein, mechanical admixture, colloid, asphalitine and big portion
Divide metal impurities；Pre- hydrofinishing is carried out in equipped with protectant reactor by the waste lubricating oil after adsorption treatment further
Imurity-removal；Entering hydrogenation main reactor through the waste lubricating oil of pre- hydrogenation carries out hydrofining reaction, makes the unreasonably in feedstock oil
Think that component is hydrogenated with saturation, product carries out fractionation cutting.Waste lubricating oil is carried out pre- hydrogenation by the method by being needed after adsorption treatment
Metallic compound is further removed, main hydrogenation reaction is then just carried out, whole process equipment investment and Operation cost comparison are high, limited
The use of the method is made.
Application No. CN103013644B discloses a kind of method that base oil is produced from waste lubricating oil, and the method includes：
In separative element, by waste lubricating oil separated, distillate I and 420~450 DEG C of distillates that boiling range is 320~450 DEG C are obtained
II；In hydrotreating unit, under hydrogen and hydrogenation conditions, distillate I and distillate II is alternately contacted with catalyst
Reaction, respectively obtains refined products I and refined products II；In steam stripping unit, respectively by the refined products I of hydrotreating and refined
Product II is stripped, and obtains lube base oil I and base oil II.The method fractionation is obtained after two cuts, without warp
Crossing adsorption treatment directly carries out hydrofinishing, and catalyst can be caused to be inactivated because of metal poisoning quickly.
US4512878 discloses a kind of method for regenerating waste lubricating oil, including：First by waste lubricating oil heat pre-treatment,
Purpose is to be dehydrated, take off light oil；Then the waste lubricating oil oil of pretreatment is carried out into separated；The oil for obtaining will be distilled again passes through one
The guard bed that individual active material is constituted, is the phosphorus and impurity for removing halogen and trace in waste lubricating oil oil mesh；
Distillate after guard bed treatment carries out hydrotreating.The method is by waste lubricating oil by being carried out at hydrogenation after related pretreatment
Reason, inactivates because of metal poisoning quickly due to by demetallated process, not will also result in catalyst.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of renovation process of waste lubricating oil, to solve present in the above method
Defect, the renovation process of described waste lubricating oil, the technique that main pretreatment and hydrofinishing using waste lubricating oil is combined
Route, there is provided a kind of investment is low, easy to operate, efficiency high waste lubricant oil regeneration new method, can not only be obtained by the method
To qualified lube base oil and blend component, and secondary pollution will not be produced in regenerative process.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme：
A kind of renovation process of waste lubricating oil, comprises the following steps：
Waste lubricating oil is dehydrated, makes water content<Filtered after 0.5wt%, primary adsorption is first carried out after filtering, then carry out
Secondary absorption, makes its content of beary metal less than 6 μ g/g, then carries out hydrogenation reaction to waste lubricating oil, obtains reclaimed oil, it is described again
Oil generation is fractionated, and can obtain low-sulphur oil, low-sulfur diesel fraction and lube base oil；
Wherein, the adsorbent of the primary adsorption is alumina adsorbant；
The adsorbent of the secondary absorption is chitosan derivatives modified inorganic adsorbent.
In waste lubricating oil except be still containing major part lubricating oil active principle, also containing some oxygenatedchemicals,
Sulfur-containing compound, nitrogen-containing compound, heavy metal, the halogen compounds of trace and the unsaturated hydrocarbons produced due to high temperature chain rupture
Etc. non-ideal component, other completely can be by Hydrobon catalyst and suitable except heavy metal for these non-ideal components
Hydrogenation conditions are removed, and after the undesirable components in waste lubricating oil are by hydrogenation saturation, reclaimed oil can reach lubrication oil base
The requirement of plinth oil or blend component.
The present invention removes the undesirable components in waste lubricating oil by the method for pretreatment and hydrofinishing, is carrying out
Before hydrofining reaction, it is necessary to carry out various pretreatments to it, the heavy metal compound that especially a large amount of additives are brought, it
Can be deposited on hydrogenation catalyst surface in hydrogenation reaction and make the quick poisoning and deactivation of catalyst.So waste lubricant oil by hydrogenation is smart
The key problem in technology of system is how to remove heavy metal and reach requirement of the Hydrobon catalyst to raw material.
Reclaimed oil is carried out into cut cutting into fractionating column after pretreatment and hydrofinishing, is cut out<170 DEG C of cut conducts
High-quality low-sulfur gasoline fraction, 170~320 DEG C of cuts as high-quality low-sulfur diesel fraction,>320 DEG C of cuts can be used as the profit of high-quality
Lubricant base oil, and it is fully able to reach the quality standard of new oil base oil.
Wherein, the operation of the dehydration, specifically includes following steps：
Waste lubricating oil is heated to 50~100 DEG C, constant temperature maintains to be dehydrated for 2~8 hours, and preferred heating-up temperature is
60~90 DEG C.
Preferably, the filtering is filtered using plate compression device.
The filtering of plate compression device is thorough.
The adsorbent of the primary adsorption is alumina adsorbant；
The adsorbent of the secondary absorption is chitosan derivatives modified adsorbent.
Preferably, the specific surface area >=200m/g of the alumina adsorbant, pore volume >=0.4ml/g.
Preferably, the reaction temperature of the primary adsorption is 80~150 DEG C, and volume space velocity is 0.3~1.2h-1；
Preferred reaction temperature is 100~120 DEG C, and volume space velocity is 0.5~1.0h-1。
Enter primary adsorption tower through the waste lubricating oil after dehydration, removing impurities matter, inhaled in the presence of primary adsorption agent
Attached treatment, realizes the removing of colloid, asphalitine and most of heavy metal, in the process the most of addition in waste lubricating oil
Agent is also removed.
Preferably, the preparation method of the chitosan derivatives modified adsorbent, specifically includes following steps：
Sorbing material is activated by roasting, acidification, then by oil soluble chitosan derivative organic solution
Fully soaked with sorbing material after activation, 45~55 DEG C of holding isothermal reaction 5~7 hours, reaction removes organic after terminating
Solvent, obtains modified sorbing material, and by modified sorbing material in placement 3~6 hours, Ran Houyan at 20~25 DEG C
Mill, sieving, obtain chitosan derivatives modified adsorbent；
It is furthermore preferred that the mass ratio of the oil soluble chitosan derivative organic solution and the sorbing material for 0.5~
3%, preferred mass ratio is 1~2%；
It is furthermore preferred that the sorbing material is the one kind in bentonite, kaolin or attapulgite, it is more preferably swollen
Profit soil；
It is furthermore preferred that the deacetylation of the oil soluble chitosan derivative is 80~95%, preferred deacetylation
It is 90%.
Its preparation method can also directly select active adsorbing material, such as atlapulgite, need not be again from atlapulgite
Directly can be reacted with chitosan derivatives by activation process.
By after the pretreatment of primary adsorption and secondary absorption, impurity, colloid, asphalitine and a huge sum of money in waste lubricating oil
Category is removed substantially, meets requirement of the hydrofinishing to raw material, other that now can make in waste lubricating oil by hydrofinishing
Non-ideal component removing or saturation, so as to reach the purpose of waste oil regeneration.
Preferably, the reaction temperature of the secondary absorption is 100~110 DEG C, and the reaction time is 1~3 hour.
Preferably, the quality of the adsorbent of the secondary absorption is the 5%~8% of the waste lubricating oil quality.
Adsorption conditionses to secondary absorption are optimized.
Preferably, the reaction temperature of the hydrogenation reaction is 280~400 DEG C, and reaction pressure is 5~15MPa, volume space velocity
It is 0.3~1.5h-1, hydrogen to oil volume ratio is 500~1200；
Preferred reaction temperature is 320~380 DEG C, and reaction pressure is 8~13MPa, and volume space velocity is 0.5~1.0h-1,
Hydrogen to oil volume ratio is 800~1000.
Preferably, the catalyst of the hydrogenation reaction is to support active component molybdenum, nickel and auxiliary agent group with alumina support
Divide P and formed, in terms of mass fraction, including：MoO320~30 parts, 2.0~7.0 parts and P of NiO2O52.0~8.0 parts；
It is furthermore preferred that specific surface area >=the 200m of the catalyst of the hydrogenation reaction2/ g, pore volume >=0.4ml/g.
In sum, the present invention uses waste lubricating oil hydrogenation of total effluent renovation process, by two-stage adsorption treatment and fixation
The refined reasonable combination of bed hydroprocessing, can effectively remove the various undesirable components in waste lubricating oil, obtain it is best in quality again
Raw lube base oil and fuel oil ingredient.The characteristics of adsorbent of the invention has good stability, activity high, long lifespan, then
Raw process does not result in environmental pollution, selects rational process route and condition, process of the invention to realize length in addition
Cycle is continuously run.
Compared with prior art, beneficial effects of the present invention are：
(1) renovation process of waste lubricating oil provided herein, pretreatment and hydrofinishing phase using waste lubricating oil
With reference to process route, there is provided a kind of investment is low, easy to operate, efficiency high waste lubricant oil regeneration new method, by the method
Qualified lube base oil and blend component is can not only obtain, and secondary pollution will not be produced in regenerative process.
(2) absorbent that the renovation process of waste lubricating oil provided herein is used, with good stability, activity
The characteristics of height, long lifespan.
Specific embodiment
Technical scheme is clearly and completely described below in conjunction with specific embodiment, but ability
Field technique personnel will be understood that, following described embodiment is a part of embodiment of the invention, rather than whole embodiments,
The present invention is merely to illustrate, and is not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belongs to the model of present invention protection
Enclose.Unreceipted actual conditions person in embodiment, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or instrument
Unreceipted production firm person, is the conventional products that can be obtained by commercially available purchase.
Embodiment 1
Taking waste lubricating oil sample 1 carries out property analysis, and analysis result is shown in Table 1.As can be seen from Table 1, waste lubricating oil tool
There is the characteristics of color is deep, acid number is high, sulfur content is high, content of beary metal is high.
The property of the waste lubricating oil sample 1 of table 1
The renovation process of the waste lubricating oil that the present embodiment is provided, specifically includes following steps：
(1) waste lubricating oil is heated to 80 DEG C of constant temperature at ambient pressure to be dehydrated within 5 hours, water content<0.5wt%, filters afterwards
Removing mechanical admixture.
(2) waste lubricating oil after filtering be pumped to filling 50ml adsorbents fixed bed reactors carry out at primary adsorption
Reason, the adsorbent is aluminum oxide, and it is shaped as column type, particle diameterHeap compares 0.52g/cm3, specific surface area
250m2/ g, pore volume 0.5ml/g.Reaction condition：Volume space velocity 0.8h-1,110 DEG C of reaction temperature, pressure is normal pressure, is inhaled through one-level
Attached oil property is shown in Table 2, it can be seen that be greatly lowered through the tenor in primary adsorption waste lubricating oil.
(3) secondary absorption treatment, secondary absorption agent are carried out into secondary absorption tower by the raw material after primary adsorption treatment
Usage amount is the 5% of waste lubricating oil, and waste lubricating oil and adsorbent are stirred under the conditions of normal pressure, 110 DEG C, and sorption reaction time 3 is small
When.3 are shown in Table through the oil property after secondary absorption, the substantially all removing of heavy metal of the oil product, heavy metal total content is less than 6 μ
g/g。
(4) waste lubricating oil from secondary absorption tower out enters the fixed bed reactors equipped with Hydrobon catalyst, this
Hydrogenation catalyst in embodiment supports active component Mo, Ni and adjuvant component P for alumina support, wherein,
MoO324.5%th, NiO 4.1%, P2O55.6%, and the catalyst pore volume 0.42ml/g, specific surface area 245m2/ g hydrogenation essences
Reaction condition processed：340 DEG C of reaction temperature, reaction pressure 8.0MPa, volume space velocity 0.8h-1, hydrogen-oil ratio 1000.Hydrofining reaction
Product afterwards cuts by cut.After the hydrogenated refining reaction of waste lubricating oil, it is full that undesirable components therein have obtained hydrogenation
With the product property of each cut is shown in Table 4.As can be seen from Table 4, waste lubricating oil is by the major product obtained after regeneration>
320 DEG C of cut, the cut fully achieves new oil base oil standard, and lube base oil standard is shown in Table 5.Remaining
Auxiliary product, 70~320 DEG C of cut can be used as low-sulfur, low solidifying fine-quality diesel oil cut.
The preparation method of the secondary absorption agent that the present embodiment is provided, specifically includes following steps：
(1) 300g attapulgites, 600g deionized waters, 30ml hydrochloric acid solutions (1 are weighed：1) in beaker, 30 points are boiled
Then clock, cooling is washed with deionized water to pH value and is about 5,420 DEG C of heat-activateds 3 hours, crushes, and crosses 200 mesh sieves, is obtained
Activation attapulgite.
(2) 30g oil soluble chitosan derivatives (deacetylation is 95%) are taken to be completely dissolved in 300g diesel oil, Ran Houjia
Enter above-mentioned 300g activation attapulgites to keep 50 DEG C of constant temperature and stir 6 hours, diesel oil is filtered to remove afterwards, and will be modified
Attapulgite is placed 4 hours at room temperature, then finely ground, the sieving of 200 mesh, obtains the attapulgite modified absorption of chitosan derivatives
Agent.
The property after primary adsorption of sample 1 of table 2
| Project | Data |
| Fe | 11.2 |
| Ni | <0.05 |
| V | <0.01 |
| Na | 5.83 |
| Ca | 287 |
| Cu | 4.02 |
| Pb | <0.05 |
| Mg | 14.3 |
| Zn | 55.2 |
| Colloid+asphalitine, w% | 0.45 |
The property after secondary absorption of sample 1 of table 3
| Project | Data |
| Fe | 0.56 |
| Ni | <0.01 |
| V | <0.01 |
| Na | 1.02 |
| Ca | 2.47 |
| Cu | <0.01 |
| Pb | <0.01 |
| Mg | 0.56 |
| Zn | 0.67 |
| Colloid+asphalitine, w% | 0.02 |
The product property of the embodiment 1 of table 4
The lubricating oil general basic oil standard of table 5
Embodiment 2
Taking waste lubricating oil sample 2 carries out property analysis, and analysis result is shown in Table 6.As can be seen from Table 6, waste lubricating oil tool
There is the characteristics of color is deep, acid number is high, sulfur content is higher, content of beary metal is higher.
The property of the waste lubricating oil sample 2 of table 6
The renovation process of the waste lubricating oil that the present embodiment is provided, specifically includes following steps：
(1) waste lubricating oil is heated to 80 DEG C of constant temperature at ambient pressure to be dehydrated within 5 hours, water content<0.5wt%, filters afterwards
Removing mechanical admixture.
(2) waste lubricating oil after filtering be pumped to filling 50ml adsorbents fixed bed reactors carry out at primary adsorption
Reason, the adsorbent is aluminum oxide, and it is shaped as column type, particle diameterHeap compares 0.56g/cm3, specific surface area
260m2/ g, pore volume 0.55ml/g.Reaction condition：Volume space velocity 0.5h-1, 120 DEG C of reaction temperature, pressure is normal pressure, is inhaled through one-level
Attached oil property is shown in Table 7, it can be seen that be greatly lowered through the tenor in primary adsorption waste lubricating oil.
(3) secondary absorption treatment, secondary absorption agent are carried out into secondary absorption tower by the raw material after primary adsorption treatment
Usage amount is the 8% of waste lubricating oil, and waste lubricating oil and adsorbent are stirred under the conditions of normal pressure, 110 DEG C, and sorption reaction time 3 is small
When.8 are shown in Table through property in the waste lubricating oil after secondary absorption, the substantially all removing of heavy metal of the oil product, heavy metal total content
Less than 6 μ g/g.
(4) waste lubricating oil from adsorption tower out enters the fixed bed reactors equipped with Hydrobon catalyst, this implementation
Hydrogenation catalyst in example supports active component Mo, Ni and adjuvant component P for alumina support, wherein, MoO325.5%th,
NiO 4.5%, P2O55.8%, and the catalyst pore volume 0.45ml/g, specific surface area 255m2/g
Hydrofining reaction condition：360 DEG C of reaction temperature, reaction pressure 10.0MPa, air speed 0.5h-1, hydrogen-oil ratio 1200.
Product after hydrofining reaction cuts by cut.After the hydrogenated refining reaction of waste lubricating oil, undesirable components therein
Hydrogenation saturation is obtained, product property is referring to table 9.
The property after primary adsorption of sample 2 of table 7
The property after secondary absorption of sample 2 of table 8
| Project | Data |
| Fe | 0.87 |
| Ni | <0.01 |
| V | <0.01 |
| Na | 2.02 |
| Ca | 1.53 |
| Cu | <0.01 |
| Pb | <0.01 |
| Mg | 0.54 |
| Zn | 0.81 |
| Colloid+asphalitine, w% | 0.03 |
The product property of the embodiment 2 of table 9
As can be seen from the table, waste lubricating oil is by the major product obtained after regeneration>320 DEG C of cut, completely may be used
To reach new oil base oil standard.Remaining auxiliary product, 170~320 DEG C of cut can be used as low-sulfur, low solidifying high-quality
Diesel oil distillate.
In sum, the present invention uses waste lubricating oil hydrogenation of total effluent renovation process, by two-stage adsorption treatment and fixation
The refined reasonable combination of bed hydroprocessing, can effectively remove the various undesirable components in waste lubricating oil, obtain it is best in quality again
Raw lube base oil and fuel oil ingredient.The characteristics of adsorbent of the invention has good stability, activity high, long lifespan, then
Raw process does not result in environmental pollution, selects rational process route and condition, process of the invention to realize length in addition
Cycle is continuously run.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that various embodiments above is only used
To illustrate technical scheme, rather than its limitations；It will be understood by those within the art that：Without departing substantially from this hair
In the case of bright spirit and scope, the technical scheme described in foregoing embodiments can be modified, or to wherein
Some or all of technical characteristic carries out equivalent；And these modifications or replacement, do not make the essence of appropriate technical solution
Depart from the scope of various embodiments of the present invention technical scheme；It is, therefore, intended that including belonging to the present invention in the following claims
In the range of all these substitutions and modifications.
Claims (10)
1. a kind of renovation process of waste lubricating oil, it is characterised in that comprise the following steps：
Waste lubricating oil is dehydrated, makes water content<Filtered after 0.5wt%, primary adsorption is first carried out after filtering, then carry out two grades
Absorption, makes its content of beary metal less than 6 μ g/g, then carries out hydrogenation reaction to waste lubricating oil, obtains reclaimed oil, the reclaimed oil
It is fractionated, low-sulphur oil, low-sulfur diesel fraction and lube base oil can be obtained；
Wherein, the adsorbent of the primary adsorption is alumina adsorbant；
The adsorbent of the secondary absorption is chitosan derivatives modified adsorbent.
2. the renovation process of waste lubricating oil according to claim 1, it is characterised in that the ratio table of the alumina adsorbant
Area >=200m/g, pore volume >=0.4ml/g.
3. the renovation process of waste lubricating oil according to claim 1, it is characterised in that the reaction temperature of the primary adsorption
It it is 80~150 DEG C, volume space velocity is 0.3~1.2h-1；
Preferred reaction temperature is 100~120 DEG C, and volume space velocity is 0.5~1.0h-1。
4. the renovation process of waste lubricating oil according to claim 1, it is characterised in that the chitosan derivatives are modified to be inhaled
Attached dose of preparation method, specifically includes following steps：
Sorbing material is activated by roasting, acidification, then by oil soluble chitosan derivative organic solution and work
Sorbing material is fully soaked after change, and 45~55 DEG C of holding isothermal reaction 5~7 hours, reaction removes organic solvent after terminating,
Obtain modified sorbing material, and by modified sorbing material in placing 3~6 hours at 20~25 DEG C, then grinding, mistake
Sieve, obtains chitosan derivatives modified adsorbent；
Preferably, the oil soluble chitosan derivative organic solution and the mass ratio of the sorbing material are 0.5~3%, more
Preferred mass ratio is 1~2%；
Preferably, the sorbing material is the one kind in bentonite, kaolin or attapulgite, more preferably bentonite；
Preferably, the deacetylation of the oil soluble chitosan derivative is 80~95%, and preferred deacetylation is 90%.
5. the renovation process of waste lubricating oil according to claim 1, it is characterised in that the operation of the dehydration, specific bag
Include following steps：
Waste lubricating oil is heated to 50~100 DEG C, constant temperature maintains to be dehydrated for 2~8 hours, preferred heating-up temperature is 60~90
℃。
6. the renovation process of waste lubricating oil according to claim 1, it is characterised in that the filtering is filled using plate compression
Put and filtered.
7. the renovation process of waste lubricating oil according to claim 1, it is characterised in that the reaction temperature of the secondary absorption
It it is 100~110 DEG C, the reaction time is 1~3 hour.
8. the renovation process of waste lubricating oil according to claim 1, it is characterised in that the adsorbent of the secondary absorption
Quality is the 5%~8% of the waste lubricating oil quality.
9. the renovation process of waste lubricating oil according to claim 1, it is characterised in that the reaction temperature of the hydrogenation reaction
It it is 280~400 DEG C, reaction pressure is 5~15MPa, volume space velocity is 0.3~1.5h-1, hydrogen to oil volume ratio is 500~1200；
Preferred reaction temperature is 320~380 DEG C, and reaction pressure is 8~13MPa, and volume space velocity is 0.5~1.0h-1, hydrogen oil body
Product is than being 800~1000.
10. the renovation process of waste lubricating oil according to claim 1, it is characterised in that the catalyst of the hydrogenation reaction
It is to be formed so that alumina support supports active component molybdenum, nickel and adjuvant component P, in terms of mass fraction, including：MoO3 20
~30 parts, 2.0~7.0 parts and P of NiO2O52.0~8.0 parts；
Preferably, the specific surface area >=200m of the catalyst of the hydrogenation reaction2/ g, pore volume >=0.4ml/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710116537.8A CN106906040B (en) | 2017-02-28 | 2017-02-28 | Regeneration method of waste lubricating oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710116537.8A CN106906040B (en) | 2017-02-28 | 2017-02-28 | Regeneration method of waste lubricating oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106906040A true CN106906040A (en) | 2017-06-30 |
| CN106906040B CN106906040B (en) | 2020-01-10 |
Family
ID=59208735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710116537.8A Active CN106906040B (en) | 2017-02-28 | 2017-02-28 | Regeneration method of waste lubricating oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106906040B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107325837A (en) * | 2017-08-14 | 2017-11-07 | 周晓红 | A kind of lube hydrotreating device of energy-conserving and environment-protective |
| CN107569901A (en) * | 2017-10-10 | 2018-01-12 | 杨继新 | Reduce oil product carbon residue device |
| CN107699330A (en) * | 2017-09-18 | 2018-02-16 | 武汉工程大学 | A kind of method for preparing anti-corrosive grease base oil using heavy-duty engine waste lubricating oil purification |
| CN112251255A (en) * | 2020-11-02 | 2021-01-22 | 尤溪县鑫辉润滑油再生利用有限公司 | Oil distillation system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998026031A1 (en) * | 1996-12-13 | 1998-06-18 | Societe Tunisienne De Lubrifiants - Sotulub | High performance method and plant for regenerating lubricating waste oil |
| CN101041789A (en) * | 2007-04-30 | 2007-09-26 | 京福马(北京)石油化工高新技术有限公司 | Waste lubricating oil hydrogenation reproducing method |
| CN104498173A (en) * | 2014-12-14 | 2015-04-08 | 创石（天津）化工有限公司 | Method for regenerating colloid-containing waste lubricating oil |
-
2017
- 2017-02-28 CN CN201710116537.8A patent/CN106906040B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998026031A1 (en) * | 1996-12-13 | 1998-06-18 | Societe Tunisienne De Lubrifiants - Sotulub | High performance method and plant for regenerating lubricating waste oil |
| CN101041789A (en) * | 2007-04-30 | 2007-09-26 | 京福马(北京)石油化工高新技术有限公司 | Waste lubricating oil hydrogenation reproducing method |
| CN104498173A (en) * | 2014-12-14 | 2015-04-08 | 创石（天津）化工有限公司 | Method for regenerating colloid-containing waste lubricating oil |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107325837A (en) * | 2017-08-14 | 2017-11-07 | 周晓红 | A kind of lube hydrotreating device of energy-conserving and environment-protective |
| CN107699330A (en) * | 2017-09-18 | 2018-02-16 | 武汉工程大学 | A kind of method for preparing anti-corrosive grease base oil using heavy-duty engine waste lubricating oil purification |
| CN107699330B (en) * | 2017-09-18 | 2021-06-01 | 武汉工程大学 | Method for purifying and preparing antirust grease base oil by using waste lubricating oil of heavy locomotive |
| CN107569901A (en) * | 2017-10-10 | 2018-01-12 | 杨继新 | Reduce oil product carbon residue device |
| CN107569901B (en) * | 2017-10-10 | 2023-01-06 | 杨继新 | Reduce oil carbon residue device |
| CN112251255A (en) * | 2020-11-02 | 2021-01-22 | 尤溪县鑫辉润滑油再生利用有限公司 | Oil distillation system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106906040B (en) | 2020-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100445355C (en) | Waste lubricating oil hydrogenation reproducing method | |
| CN106906040A (en) | A kind of renovation process of waste lubricating oil | |
| KR840001581B1 (en) | Manufacture of hydrocracked low pour lubricating oils | |
| CN108085060A (en) | Waste lubricant oil by hydrogenation process for purification and hydrofinishing system | |
| CN105733793B (en) | A kind of waste lubricating oil hydrogenation reproducing method | |
| JP2620811B2 (en) | How to remove mercury and possibly arsenic in hydrocarbons | |
| CN101120075B (en) | Process for producing ultra low sulfur and low aromatic diesel fuel | |
| JPS6011586A (en) | Catalytic hydrodecomposition | |
| CN105647573A (en) | Method for producing light-weight aromatic hydrocarbons and clean fuel oil by moving bed hydrocracking | |
| CN105505550B (en) | A kind of method of waste lubricant oil regeneration processing | |
| CN103305269B (en) | Method for producing gasoline and diesel by directly hydrogenating medium and low temperature coal tar | |
| CN107418621A (en) | The method for removing metallic compound in waste lubricating oil | |
| CN107254330A (en) | A kind of waste lubricating oil perhydro method produces the process engineering for regenerating of high-grade low-freezing lube base oil | |
| CN103013644B (en) | Method for producing base oil from waste lubricating oil | |
| CN105793396A (en) | Method for hydrotreating diesel fuel in reactors in series, comprising hydrogen recirculation | |
| JP2003522819A (en) | Integrated manufacturing method for converting natural gas and gas field condensates into high value liquid products | |
| CN104962314A (en) | System and method for producing raw material of needle coke by oil slurry | |
| CN102876367A (en) | Deep desulphurization dearomatization combination method of diesel oil | |
| CN101314735A (en) | Hydrogenation method for reducing aromatic hydrocarbon content of diesel oil cut fraction and improving its cetane number | |
| CN108329945B (en) | Preparation method of transformer oil anti-gassing component | |
| CN104673378B (en) | A kind of production method of sulfur-free gasoline | |
| CN102453537A (en) | Method for maximum production of clean diesel oil by shale oil whole fraction hydrogenation | |
| CN104673376B (en) | A kind of gasoline desulfating method | |
| EP3533856B1 (en) | Method for preparing hexadecahydropyrene | |
| CN1718689A (en) | Pretreatment method of lubricating oil hydrogenation isomeric dewax raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |