CN106906040B - Regeneration method of waste lubricating oil - Google Patents
Regeneration method of waste lubricating oil Download PDFInfo
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- CN106906040B CN106906040B CN201710116537.8A CN201710116537A CN106906040B CN 106906040 B CN106906040 B CN 106906040B CN 201710116537 A CN201710116537 A CN 201710116537A CN 106906040 B CN106906040 B CN 106906040B
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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
- C10M175/0008—Working-up used lubricants to recover useful products ; Cleaning with the use of adsorbentia
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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
- C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
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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
- 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
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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
- 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
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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
- C10M175/0058—Working-up used lubricants to recover useful products ; Cleaning by filtration and centrifugation processes; apparatus therefor
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Abstract
The invention provides a regeneration method of waste lubricating oil, which comprises the steps of dehydrating the waste lubricating oil, filtering after the water content is less than 0.5 wt%, carrying out primary adsorption after filtering, carrying out secondary adsorption again to ensure that the heavy metal content is less than 6 mu g/g, carrying out hydrogenation reaction on the waste lubricating oil to obtain regenerated oil, and fractionating the regenerated oil to obtain low-sulfur gasoline, low-sulfur diesel fraction and lubricating oil base oil; wherein, the adsorbent of the first-stage adsorption is alumina adsorbent; the adsorbent for the second-stage adsorption is a chitosan derivative modified adsorbent. The invention can effectively remove various non-ideal components in the waste lubricating oil and obtain the components of the base oil and the fuel oil of the regenerated lubricating oil with excellent quality. The adsorbent of the invention has the characteristics of good stability, high activity and long service life, does not cause environmental pollution in the regeneration process, and selects reasonable process routes and conditions.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a regeneration method of waste lubricating oil.
Background
In recent years, the amount of lubricating oil used has increased year by year with the rapid increase in the stock of the china automobile market. At present, the usage amount of lubricating oil in China reaches 760 ten thousand tons per year, the lubricating oil consumption is increased at a speed of 24% per year, the discharge amount of waste lubricating oil reaches more than 500 ten thousand tons per year, the lubricating oil demand in China is expected to be doubled by 2020, and China finally becomes the first major country for generating the waste lubricating oil in the world. Lubricating oil produces a large amount of colloid and oxide due to external pollution in the working process, so that the effects of controlling friction, reducing abrasion, cooling and the like are reduced and even lost, but the main components of the lubricating oil are not changed, and if waste oil is discarded or combusted, not only is energy greatly wasted, but also serious environmental pollution is caused. With the increasing exhaustion of petroleum resources, the increasing awareness of environmental protection and the increasing price of oil, the recycling of waste lubricating oil is highly regarded by various countries in the world.
The impurities contained in the used lubricating oil are generally mainly: water, impurities (such as dust, asphaltenes, metals from abrasion), light components (such as mixed gasoline and diesel fuel, lubricating oil chain scission products), lubricating oil additives and decomposition products, and partially deteriorated components (such as unsaturated hydrocarbons from chain scission of lubricating oil molecules, alcohols and acids from oxidation). Most of the hydrocarbons (about 90%) in the used lubricating oil are not deteriorated and can be recycled. By removing impurities and properly treating the deteriorated components, the waste lubricating oil can be recycled and even regenerated into high-quality lubricating oil base oil. Therefore, the regeneration and recovery of the waste lubricating oil can not only protect the environment, but also realize the resource recycling and have good social and economic benefits.
Along with the continuous improvement of the quality specification and standard of the lubricating oil, the types and the dosage of additives in the lubricating oil are also continuously increased, and the difficulty of the process for recycling the regenerated waste lubricating oil is increased; meanwhile, with the stricter environmental regulations, the technology of generating secondary pollution in the waste oil regeneration technology is gradually eliminated, and the common technology such as an acid-clay refining type waste lubricating oil recovery process can generate a large amount of acid, waste clay and waste water in the recovery process, and the product quality provided by the process is poor and can not reach the standard of the existing lubricating oil base oil, so that the conditions promote the appearance of a more advanced waste oil process. The waste oil hydrorefining process has become a new technology for replacing acid-clay refining and solvent extraction processes because of higher environmental protection, economy and operability.
The patent with publication number CN1132922C discloses a combined process for recovering waste lubricating oil, which adopts a suspension bed hydrogenation process, and uses metal chips and compounds of crude oil in the waste oil as catalysts to carry out hydrogenation treatment on the waste oil, and then the regenerated base oil and the byproduct light oil can be obtained through simple filtration, distillation, fixed bed hydrorefining and light component product separation. The method has the disadvantages that the metal compounds in the waste oil are mainly the decomposition products of lubricating oil additives such as calcium, magnesium, zinc and the like, and the metal compounds hardly have catalytic action on hydrogenation reaction, so that the hydrogenation process cannot effectively remove heteroatoms such as S, N, O in the waste oil.
Application number CN200710098992.6 discloses a spent lubricating oil hydrogenation regeneration method. The method mainly comprises the steps of dehydrating, filtering and adsorbing the raw material waste lubricating oil to remove water, mechanical impurities, colloid, asphaltene and most of metal impurities; the waste lubricating oil after adsorption treatment is pre-hydrogenated and refined in a reactor filled with a protective agent to further remove impurities; the pre-hydrogenated waste lubricating oil enters a hydrogenation main reactor to carry out hydrofining reaction, so that non-ideal components in the raw oil are subjected to hydrogenation saturation, and products are subjected to fractionation and cutting. The method is characterized in that the waste lubricating oil is subjected to adsorption treatment, then is subjected to pre-hydrogenation to further remove metal compounds, and then is subjected to main hydrogenation reaction, so that the equipment investment and the operation cost in the whole process are high, and the use of the method is limited.
Application No. CN103013644B discloses a method for producing base oil from waste lubricating oil, which comprises: in a separation unit, the waste lubricating oil is subjected to distillation separation to obtain a distillate I with the distillation range of 320-450 ℃ and a distillate II with the distillation range of 420-450 ℃; in a hydrotreating unit, under the conditions of hydrogen and hydrogenation reaction, alternately contacting and reacting a distillate I and a distillate II with a catalyst to respectively obtain a refined product I and a refined product II; and in a stripping unit, respectively stripping the hydrotreated refined product I and the hydrotreated refined product II to obtain the lubricating oil base oil I and the lubricating oil base oil II. The method can cause the catalyst to be quickly deactivated due to metal poisoning by directly carrying out hydrofining without adsorption treatment after two fractions are obtained by fractionation.
US4512878 discloses a method for regenerating used lubricating oil comprising: firstly, heating the waste lubricating oil for pretreatment, and aiming at dehydrating and removing light oil; then, distilling and separating the pretreated waste lubricating oil; then the oil obtained by distillation passes through a protective bed formed by active substances, so as to remove halogen elements, trace phosphorus and impurities in the waste lubricating oil; and (4) carrying out hydrotreating on the distillate after the guard bed treatment. The method carries out hydrotreating after the relevant pretreatment of the waste lubricating oil, and can also cause the catalyst to be quickly deactivated due to metal poisoning because of no demetallization process.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention provides a method for regenerating waste lubricating oil, which mainly adopts a process route of combining pretreatment and hydrofining of the waste lubricating oil, and provides a novel method for regenerating the waste lubricating oil, which has low investment, simple and convenient operation and high efficiency.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a method of regenerating a used lubricating oil, comprising the steps of:
dehydrating the waste lubricating oil, filtering after the water content is less than 0.5 wt%, performing primary adsorption and secondary adsorption after filtering to ensure that the heavy metal content is less than 6 mu g/g, performing hydrogenation reaction on the waste lubricating oil to obtain regenerated oil, and fractionating the regenerated oil to obtain low-sulfur gasoline, low-sulfur diesel fraction and lubricating oil base oil;
wherein the adsorbent of the first-stage adsorption is alumina adsorbent;
the adsorbent for the secondary adsorption is a chitosan derivative modified inorganic adsorbent.
The waste lubricating oil contains most of the effective components still used as lubricating oil, and also contains some non-ideal components such as oxygen-containing compounds, sulfur-containing compounds, nitrogen-containing compounds, heavy metals, trace halogen compounds and unsaturated hydrocarbons generated by high-temperature chain scission, the non-ideal components except the heavy metals can be completely removed by a hydrofining catalyst and proper hydrogenation reaction conditions, and after the non-ideal components in the waste lubricating oil are subjected to hydrogenation saturation, the regenerated oil can meet the requirements of lubricating oil base oil or blending components.
The method removes non-ideal components in the waste lubricating oil by a pretreatment and hydrofining method, and various pretreatments must be carried out on the waste lubricating oil before the hydrofining reaction is carried out, particularly heavy metal compounds brought by a large amount of additives, which are deposited on the surface of a hydrogenation catalyst during the hydrogenation reaction to quickly poison and deactivate the catalyst. Therefore, the key point of the technology of the hydrofining of the waste lubricating oil lies in how to remove heavy metals to meet the requirements of the hydrofining catalyst on raw materials.
After pretreatment and hydrofining, the reclaimed oil enters a fractionating tower for fraction cutting, a fraction at the temperature of 170 ℃ is cut out to be used as a high-quality low-sulfur gasoline fraction, a fraction at the temperature of 170-320 ℃ is used as a high-quality low-sulfur diesel fraction, and a fraction at the temperature of 320 ℃ can be used as high-quality lubricating oil base oil and can completely reach the quality standard of new lubricating oil base oil.
The dehydration operation specifically comprises the following steps:
heating the waste lubricating oil to 50-100 ℃, maintaining the constant temperature for 2-8 hours for dehydration, and preferably heating the waste lubricating oil to 60-90 ℃.
Preferably, the filtration is performed by adopting a plate-and-frame filter pressing device.
The plate frame filter pressing device can filter thoroughly.
The first-stage adsorption adsorbent is an alumina adsorbent;
the adsorbent for the secondary adsorption is a chitosan derivative modified adsorbent.
Preferably, the specific surface area of the alumina adsorbent is more than or equal to 200m/g, and the pore volume is more than or equal to 0.4 ml/g.
Preferably, the reaction temperature of the primary adsorption is 80-150 ℃, and the volume space velocity is 0.3-1.2 h-1；
More preferably, the reaction temperature is 100-120 ℃, and the volume space velocity is 0.5-1.0 h-1。
The waste lubricating oil after dehydration and impurity removal enters a first-stage adsorption tower, and is subjected to adsorption treatment under the action of a first-stage adsorbent, so that removal of colloid, asphaltene and most heavy metals is realized, and most additives in the waste lubricating oil are also removed in the process.
Preferably, the preparation method of the chitosan derivative modified adsorbent specifically comprises the following steps:
roasting and acidifying an adsorbing material to activate, fully soaking an oil-soluble chitosan derivative organic solution and the activated adsorbing material, reacting at a constant temperature of 45-55 ℃ for 5-7 hours, removing the organic solvent after the reaction is finished to obtain a modified adsorbing material, placing the modified adsorbing material at 20-25 ℃ for 3-6 hours, grinding and sieving to obtain a chitosan derivative modified adsorbing agent;
more preferably, the mass ratio of the oil-soluble chitosan derivative organic solution to the adsorbing material is 0.5-3%, and more preferably 1-2%;
more preferably, the adsorbing material is one of bentonite, kaolin or attapulgite, and more preferably bentonite;
more preferably, the degree of deacetylation of the oil-soluble chitosan derivative is 80-95%, and more preferably 90%.
The preparation method can also directly select active adsorption material, such as activated clay, which can directly react with chitosan derivative without activation treatment.
After the pretreatment of the first-stage adsorption and the second-stage adsorption, impurities, colloid, asphaltene and heavy metals in the waste lubricating oil are basically removed, the requirement of hydrofining on raw materials is met, and other non-ideal components in the waste lubricating oil can be removed or saturated through hydrofining, so that the aim of waste oil regeneration is fulfilled.
Preferably, the reaction temperature of the secondary adsorption is 100-110 ℃, and the reaction time is 1-3 hours.
Preferably, the mass of the secondary adsorption adsorbent is 5-8% of the mass of the waste lubricating oil.
And optimizing the adsorption condition of the secondary adsorption.
Preferably, the reaction temperature of the hydrogenation reaction is 280-400 ℃, the reaction pressure is 5-15 MPa, and the volume space velocity is 0.3-1.5 h-1The volume ratio of hydrogen to oil is 500-1200;
more preferably, the reaction temperature is 320-380 ℃, the reaction pressure is 8-13 MPa, and the volume space velocity is 0.5-1.0 h-1The volume ratio of hydrogen to oil is 800-1000.
Preferably, the catalyst for the hydrogenation reaction is formed by an alumina carrier supporting active components of molybdenum and nickel and an auxiliary component P, and comprises the following components in parts by mass: MoO320-30 parts of NiO 2.0-7.0 parts of P2O52.0-8.0 parts;
more preferably, the specific surface area of the catalyst for the hydrogenation reaction is more than or equal to 200m2The pore volume is more than or equal to 0.4 ml/g.
In conclusion, the method adopts the full fraction hydrogenation regeneration method of the waste lubricating oil, and can effectively remove various non-ideal components in the waste lubricating oil through the reasonable combination of two-stage adsorption treatment and fixed bed hydrofining, so as to obtain the regenerated lubricating oil base oil and fuel oil components with excellent quality. The adsorbent has the characteristics of good stability, high activity and long service life, does not cause environmental pollution in the regeneration process, and can realize long-period continuous operation by selecting reasonable process routes and conditions.
Compared with the prior art, the invention has the beneficial effects that:
(1) the regeneration method of the waste lubricating oil provided by the application adopts a process route combining pretreatment and hydrofining of the waste lubricating oil, and provides a novel method for regenerating the waste lubricating oil, which has the advantages of low investment, simple and convenient operation and high efficiency.
(2) The absorbent used in the regeneration method of the waste lubricating oil provided by the application has the characteristics of good stability, high activity and long service life.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The waste lubricating oil sample 1 was subjected to property analysis, and the analysis results are shown in Table 1. As can be seen from Table 1, the waste lubricating oil has the characteristics of dark color, high acid value, high sulfur content and high heavy metal content.
TABLE 1 Properties of used lubricating oil sample 1
The method for regenerating the used lubricating oil provided by the embodiment specifically comprises the following steps:
(1) heating the waste lubricating oil to 80 ℃ under normal pressure, keeping the temperature constant for 5 hours for dehydration, and filtering to remove mechanical impurities, wherein the water content is less than 0.5 wt%.
(2) Pumping the filtered waste lubricating oil to a fixed bed reactor filled with 50ml of adsorbent for primary adsorption treatment, wherein the adsorbent is aluminum oxide, is in the shape of a column and has a particle size
The bulk ratio is 0.52g/cm3Specific surface area of 250m2The pore volume is 0.5 ml/g. Reaction conditions are as follows: the volume space velocity is 0.8h < -1 >, the reaction temperature is 110 ℃, the pressure is normal pressure, the properties of the oil product after primary adsorption are shown in a table 2, and the metal content in the waste lubricating oil after the primary adsorption is greatly reduced.
(3) The raw material after the first-stage adsorption treatment enters a second-stage adsorption tower for second-stage adsorption treatment, the using amount of a second-stage adsorbent is 5% of that of the waste lubricating oil, the waste lubricating oil and the adsorbent are stirred under the conditions of normal pressure and 110 ℃, and the adsorption reaction time is 3 hours. The properties of the oil product after the secondary adsorption are shown in a table 3, the heavy metals of the oil product are basically completely removed, and the total content of the heavy metals is less than 6 microgram/g.
(4) The waste lubricating oil from the second-stage adsorption tower enters a fixed bed reactor filled with a hydrofining catalyst, the hydrofining catalyst in the embodiment is an alumina carrier loaded with active components Mo and Ni and an auxiliary agent component P, wherein the MoO324.5％、NiO 4.1％、P2O55.6 percent, the pore volume of the catalyst is 0.42ml/g, and the specific surface area is 245m2The reaction conditions of the hydrorefining are as follows: the reaction temperature is 340 ℃, the reaction pressure is 8.0MPa, and the volume space velocity is 0.8h-1The hydrogen-oil ratio is 1000. The product after the hydrofinishing reaction is cut. After the waste lubricating oil is subjected to hydrofining reaction, the non-ideal components in the waste lubricating oil are subjected to hydrogenation saturation, and the fractions areThe product properties are shown in Table 4. As can be seen from Table 4, the main product obtained after regeneration of the used lubricating oil is>The fraction at 320 ℃ can completely reach the new lubricating base oil standard, and the lubricating base oil standard is shown in Table 5. The rest of the secondary products, the fraction at 70-320 ℃ can be used as high-quality diesel oil fraction with low sulfur and low condensation point.
The preparation method of the secondary adsorbent provided by the embodiment specifically includes the following steps:
(1) 300g of attapulgite, 600g of deionized water and 30ml of hydrochloric acid solution (1: 1) are weighed in a beaker, boiled for 30 minutes, cooled, washed by deionized water until the pH value is about 5, heated and activated for 3 hours at 420 ℃, crushed and sieved by a 200-mesh sieve to prepare the activated attapulgite.
(2) 30g of oil-soluble chitosan derivative (the deacetylation degree is 95%) is fully dissolved in 300g of diesel oil, then 300g of the activated attapulgite is added, the temperature is kept constant at 50 ℃, the mixture is stirred for 6 hours, then the diesel oil is filtered and removed, the modified attapulgite is placed at room temperature for 4 hours, and then the mixture is ground and sieved by a 200-mesh sieve, so that the chitosan derivative modified attapulgite adsorbent is obtained.
TABLE 2 Properties of sample 1 after first-order adsorption
| Item | Data of |
| Metal, μ g--1 | |
| 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 |
| Gelatine + asphaltene, w% | 0.45 |
TABLE 3 Properties of sample 1 after second stage adsorption
| Item | Data of |
| Metal, μ g--1 | |
| 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 |
| Gelatine + asphaltene, w% | 0.02 |
Table 4 product properties of example 1
TABLE 5 Universal base oil Standard for lubricating oils
Example 2
The waste lubricating oil sample 2 was subjected to property analysis, and the analysis results are shown in Table 6. As can be seen from Table 6, the used lubricating oil has the characteristics of dark color, high acid value, higher sulfur content and higher heavy metal content.
TABLE 6 Properties of used lubricating oil sample 2
The method for regenerating the used lubricating oil provided by the embodiment specifically comprises the following steps:
(1) heating the waste lubricating oil to 80 ℃ under normal pressure, keeping the temperature constant for 5 hours for dehydration, and filtering to remove mechanical impurities, wherein the water content is less than 0.5 wt%.
(2) Pumping the filtered waste lubricating oil to a fixed bed reactor filled with 50ml of adsorbent for primary adsorption treatment, wherein the adsorbent is aluminum oxide, is in the shape of a column and has a particle sizePile ratio of 0.56g/cm3Specific surface area 260m2The pore volume is 0.55 ml/g. Reaction conditions are as follows: volume space velocity of 0.5h-1The reaction temperature is 120 ℃, the pressure is normal pressure, the properties of the oil product after primary adsorption are shown in table 7, and it can be seen that the metal content in the waste lubricating oil is greatly reduced through the primary adsorption.
(3) The raw material after the first-stage adsorption treatment enters a second-stage adsorption tower for second-stage adsorption treatment, the using amount of a second-stage adsorbent is 8% of that of the waste lubricating oil, the waste lubricating oil and the adsorbent are stirred under the conditions of normal pressure and 110 ℃, and the adsorption reaction time is 3 hours. The properties of the waste lubricating oil after the secondary adsorption are shown in a table 8, the heavy metals of the oil product are basically completely removed, and the total content of the heavy metals is less than 6 mu g/g.
(4) The waste lubricating oil from the adsorption tower enters a fixed bed reactor filled with a hydrofining catalyst, the hydrofining catalyst in the embodiment is an alumina carrier loaded with active components Mo and Ni and an auxiliary agent component P, wherein MoO325.5％、NiO 4.5％、P2O55.8 percent, the pore volume of the catalyst is 0.45ml/g, and the specific surface area is 255m2/g
And (3) hydrofining reaction conditions: the reaction temperature is 360 ℃, the reaction pressure is 10.0MPa, and the space velocity is 0.5h-1And hydrogen to oil ratio of 1200. The product after the hydrofinishing reaction is cut. After the used lubricating oil is subjected to hydrofining reaction, the non-ideal components in the used lubricating oil are subjected to hydrogenation saturation, and the product properties are shown in Table 9.
TABLE 7 Properties of sample 2 after first-order adsorption
TABLE 8 sample 2 Properties after second stage adsorption
| Item | Data of |
| Metal, μ g--1 | |
| 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 |
| Gelatine + asphaltene, w% | 0.03 |
Table 9 product properties of example 2
As can be seen from the table, the main product obtained after the regeneration of the used lubricating oil is the fraction of >320 ℃, and can completely reach the standard of the new lubricating oil base oil. The rest of the secondary products, namely the distillate at 170-320 ℃ can be used as high-quality diesel oil distillate with low sulfur and low condensation point.
In conclusion, the method adopts the full fraction hydrogenation regeneration method of the waste lubricating oil, and can effectively remove various non-ideal components in the waste lubricating oil through the reasonable combination of two-stage adsorption treatment and fixed bed hydrofining, so as to obtain the regenerated lubricating oil base oil and fuel oil components with excellent quality. The adsorbent has the characteristics of good stability, high activity and long service life, does not cause environmental pollution in the regeneration process, and can realize long-period continuous operation by selecting reasonable process routes and conditions.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.
Claims (19)
1. A method for regenerating a used lubricating oil, comprising the steps of:
dehydrating the waste lubricating oil, filtering after the water content is less than 0.5 wt%, performing primary adsorption and secondary adsorption after filtering to ensure that the heavy metal content is less than 6 mu g/g, performing hydrogenation reaction on the waste lubricating oil to obtain regenerated oil, and fractionating the regenerated oil to obtain low-sulfur gasoline, low-sulfur diesel fraction and lubricating oil base oil;
wherein the adsorbent of the first-stage adsorption is alumina adsorbent;
the secondary adsorption adsorbent is a chitosan derivative modified adsorbent;
the preparation method of the chitosan derivative modified adsorbent specifically comprises the following steps:
roasting and acidifying the adsorbing material to activate, fully soaking the oil-soluble chitosan derivative organic solution and the activated adsorbing material, reacting at a constant temperature of 45-55 ℃ for 5-7 hours, removing the organic solvent after the reaction is finished to obtain a modified adsorbing material, placing the modified adsorbing material at 20-25 ℃ for 3-6 hours, grinding and sieving to obtain the chitosan derivative modified adsorbing agent.
2. The method for regenerating used lubricating oil according to claim 1, wherein the specific surface area of the alumina adsorbent is 200m/g or more and the pore volume is 0.4ml/g or more.
3. The method for regenerating the used lubricating oil according to claim 1, wherein the reaction temperature of the primary adsorption is 80 to 150 ℃, and the volume space velocity is 0.3 to 1.2h-1。
4. The method for regenerating the used lubricating oil according to claim 1, wherein the reaction temperature of the primary adsorption is 100 to 120 ℃, and the volume space velocity is 0.5 to 1.0h-1。
5. The method for regenerating a used lubricating oil according to claim 1, wherein the mass ratio of the oil-soluble chitosan derivative organic solution to the adsorbing material is 0.5 to 3%.
6. The method for regenerating a used lubricating oil according to claim 1, wherein the mass ratio of the oil-soluble chitosan derivative organic solution to the adsorbent is 1 to 2%.
7. The method for regenerating used lubricating oil according to claim 1, wherein the adsorbent is one of bentonite, kaolin, or attapulgite.
8. The method for regenerating used lubricating oil according to claim 1, wherein the adsorbent is bentonite.
9. The method for regenerating used lubricating oil according to claim 1, wherein the degree of deacetylation of the oil-soluble chitosan derivative is 80 to 95%.
10. The method for regenerating used lubricating oil according to claim 1, wherein the degree of deacetylation of the oil-soluble chitosan derivative is 90%.
11. The method for regenerating used lubricating oil according to claim 1, characterized in that the operation of dehydration specifically comprises the steps of:
heating the waste lubricating oil to 50-100 ℃, and maintaining the constant temperature for 2-8 hours for dehydration.
12. The method for regenerating used lubricating oil according to claim 11, wherein the heating temperature is 60 to 90 ℃.
13. The method for regenerating used lubricating oil according to claim 1, wherein the filtration is performed by a plate-and-frame filter press device.
14. The method for regenerating used lubricating oil according to claim 1, wherein the reaction temperature of the secondary adsorption is 100 to 110 ℃ and the reaction time is 1 to 3 hours.
15. The method for regenerating used lubricating oil according to claim 1, wherein the mass of the secondary adsorbent is 5% to 8% of the mass of the used lubricating oil.
16. The method for regenerating the used lubricating oil according to claim 1, wherein the reaction temperature of the hydrogenation reaction is 280 to 400 ℃, the reaction pressure is 5 to 15MPa, and the volume space velocity is 0.3 to 1.5h-1The volume ratio of hydrogen to oil is 500-1200.
17. The method for regenerating the used lubricating oil according to claim 1, wherein the reaction temperature of the hydrogenation reaction is 320 to 380 ℃, the reaction pressure is 8 to 13MPa, and the volume space velocity is 0.5 to 1.0h-1The volume ratio of hydrogen to oil is 800-1000.
18. The method for regenerating the used lubricating oil according to claim 1, wherein the catalyst for the hydrogenation reaction is formed by loading active components molybdenum and nickel and an auxiliary component P on an alumina carrier, and comprises the following components in parts by mass: MoO320-30 parts of NiO 2.0-7.0 parts of P2O52.0 to 8.0 parts.
19. The method for regenerating used lubricating oil according to claim 1, wherein the catalyst for the hydrogenation reaction has a specific surface area of 200m or more2The pore volume is more than or equal to 0.4 ml/g.
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| 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 |
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| WO1998026031A1 (en) * | 1996-12-13 | 1998-06-18 | Societe Tunisienne De Lubrifiants - Sotulub | High performance method and plant for regenerating lubricating waste oil |
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