CN115820333B - Recycling recycling method of waste lubricating oil sludge - Google Patents
Recycling recycling method of waste lubricating oil sludge Download PDFInfo
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- 239000002699 waste material Substances 0.000 title claims abstract description 62
- 239000010802 sludge Substances 0.000 title claims abstract description 60
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000004064 recycling Methods 0.000 title claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 14
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- 238000001035 drying Methods 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 238000009835 boiling Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- 230000001050 lubricating effect Effects 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 abstract description 42
- 239000012071 phase Substances 0.000 abstract description 33
- 239000007789 gas Substances 0.000 abstract description 23
- 229910052742 iron Inorganic materials 0.000 abstract description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008929 regeneration Effects 0.000 abstract description 7
- 238000011069 regeneration method Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
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- 239000007787 solid Substances 0.000 description 10
- 239000002923 metal particle Substances 0.000 description 9
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 8
- 229960001180 norfloxacin Drugs 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
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- 238000011084 recovery Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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Abstract
The invention relates to a recycling method of waste lubricating oil sludge, which comprises the following steps: (1) Reacting the waste lubricating oil sludge in a water gas atmosphere, and carrying out solid-liquid separation after the reaction is completed; (2) And distilling the obtained liquid phase to obtain regenerated lubricating oil base oil, and drying the obtained solid phase product to obtain iron powder particles. In the invention, carbon monoxide in the water gas has strong interaction with iron phase in the waste lubricating oil sludge, so that the iron powder which is difficult to separate originally can be separated from the oil phase through solid-liquid separation means such as simple filtration, the oil content in the separated iron powder is very low, and the separated iron powder can be directly used as industrial raw materials or catalysts and has very excellent performance. Compared with pure hydrogen, the water gas has low cost, can further reduce the production cost and improve the profit margin of the regeneration process.
Description
Technical Field
The invention relates to a recycling method of waste lubricating oil sludge, and belongs to the field of recycling of dangerous waste.
Background
With the rapid development of fields such as mechanical engineering, the use amount of lubricating oil is increasing. Taking plate processing as an example, the lubricating oil (namely rolling oil) with lubricating and cooling effects is used in a considerable amount in the rolling process of the steel plate. In the actual production process, the high-temperature and high-pressure operation conditions can lead to oxidation, isomerization and other reactions of the rolling oil, and in addition, fine metal particles generated in the rolling friction process can be mixed into the rolling oil, so that the rolling oil gradually loses the effects of lubrication, protection and the like and is finally converted into waste rolling oil. After the waste rolling oil is subjected to primary recovery of part of oil liquid by the separating device, a large amount of waste lubricating oil sludge, namely waste rolling oil sludge, is formed. In addition, in the machining process, such as cutting and the like, lubricating oil also changes quality after repeated recycling, a large amount of metal particles are mixed, and a large amount of waste lubricating oil sludge is generated after simple separation. The waste lubricating oil sludge cannot be directly used for production, belongs to industrial waste, and can destroy the vegetation structure of the land, pollute air and water body and seriously threaten the natural environment by direct discharge.
The contents of oil and iron in the two waste lubricating oil sludge are higher, wherein the oil phase is not completely deteriorated oil, and the truly deteriorated base oil only occupies a small part of the whole body, so the waste lubricating oil sludge has very high recycling value; the iron phase is iron particles with very small particle size and has very strong practical utilization value. Therefore, the waste lubricating sludge is a waste resource with high recycling value. At present, the treatment approaches for the waste lubricating oil sludge containing metal particles mainly comprise solvent extraction, heat treatment (incineration, thermal analysis and the like), ultrasonic or microwave separation, flocculation, membrane separation and the like, but the various treatment methods have certain problems, such as secondary pollution of an extractant caused by solvent extraction; the methods such as ultrasonic and microwave are high in cost, and industrial mass production is difficult to realize; the heat treatment not only causes air pollution, but also wastes precious oily resources in the waste lubricating oil sludge; the flocculation process can only treat samples with lower solid content; membrane separation algorithms face severe membrane fouling and are limited by very low membrane flux. Therefore, the current various treatment technologies cannot meet the actual production requirements, and therefore development of a treatment technology which is simple to operate, low in cost, environment-friendly and pollution-free is needed to realize the recycling of oil liquid and metal particles in the waste lubricating oil sludge.
US3471533a discloses a process for treating waste fat rolling oil sludge to recover oil therein, the sludge consisting of a relatively permanent emulsion of oil, water and iron contaminants, the process comprising: (1) The sludge is treated with an inorganic acid in an amount between about 5% and 100% of that theoretically required to react with the iron, and the temperature is raised to about 110 to about 215°f. At a temperature of about 110 to about 215°f, a macroscopic single "sludge-acid" mixture is obtained, (2) the "sludge-acid" mixture is filtered through a porous filter material to obtain an emulsion effluent, (3) the freshly filtered emulsion effluent appears as an emulsion, but quickly delaminates under the action of gravity, and an oil phase and an oil-free aqueous phase are obtained after the operations such as gravity sedimentation or centrifugal separation, thereby achieving the recovery of the oil. However, this method does not recover the iron content of the waste rolling sludge and generates a large amount of acid-containing and heavy metal-containing wastewater which needs further treatment.
CN109721216a discloses a process and a device for pollution-free treatment of waste rolling oil sludge, the waste rolling oil sludge can be treated by the device to realize recycling of solvent, and separated iron powder is completely free of oil. The process structure comprises the following steps: mixing unit, filtration unit, concentration unit, distillation unit and drying unit. However, the high solid content in the waste rolled sludge results in high resistance of the filtering unit, and the clear liquid obtained by filtering needs to be subjected to flash evaporation for multiple times to realize separation of the solid phase and the oil phase in the sludge, so that the energy consumption is high. In addition, the use amount of the core solvent is also large and is 1.0 to 5.0 times of the mass of the waste oil sludge, so that very high requirements are put on the treatment capacity, the occupied area and the like of equipment.
In the field of regeneration of used lubricating oils, hydrofining has been widely used in recent years as a representative of a pollution-free regeneration refining process. However, the hydrogenation process has high requirements on raw material quality, and has the problems of high operation cost, low profit margin and the like due to the high-temperature and high-pressure operation condition, so that the hydrogenation process cannot be applied to recycling of waste lubricating oil sludge. How to reduce the cost of the regeneration process and improve the profit margin of the process becomes a key for promoting the recycling of the waste lubricating oil sludge.
Disclosure of Invention
Aiming at the characteristics of insufficient and waste lubricating oil sludge in the prior art, the invention provides a waste lubricating oil sludge resource using water gas as raw materialA method for recycling and reutilizing. In the invention, carbon monoxide (CO) in the water gas has strong interaction with an iron phase, so that the nanoscale iron powder which is difficult to separate originally can be separated from an oil phase through solid-liquid separation means such as simple filtration, the oil content in the separated iron powder is very low, and the separated iron powder can be directly used as an iron powder raw material for industrial production or used as a catalyst. While hydrogen (H) in water gas 2 ) The method can convert colloid, asphaltene, organic acid and other impurities in the waste lubricating oil into base oil components or light hydrocarbons, thereby improving the regeneration yield and quality of the lubricating oil, and obtaining the lubricating oil base oil with good performance through distillation of a liquid phase after solid-liquid separation. Therefore, the invention can realize the recycling of the waste lubricating oil sludge.
Description of the terminology:
waste lubricating oil sludge: the waste lubricating oil sludge refers to waste lubricating oil sludge rich in metal particles, and particularly refers to waste lubricating oil sludge generated in a steel plate rolling process or a machining process and the like. The waste lubricating oil sludge generated in the steel plate rolling process, namely waste rolling oil sludge, is rolling oil which plays roles in lubrication, cooling and the like in the steel plate cold rolling process, is changed after multiple rolling operations and the like, is mixed with a large amount of metal particles, and is oily sludge obtained after the primary recovery of part of oil. The waste lubricating sludge generated in the machining process refers to oily sludge obtained by recycling lubricating oil used in cutting and other operations for a plurality of times, deteriorating the lubricating oil, mixing a large amount of metal particles and primarily recycling part of the oil. The waste lubricating oil sludge contains partially deteriorated lubricating oil, water, colloid, asphaltene and other organic matters and a large amount of solid-phase metal particles. It should be noted that the waste lubricating sludge according to the present invention is not limited to the above two types of waste lubricating sludge, and any type of waste lubricating sludge rich in metal particles falls within the scope of the present invention.
Water gas: the water gas refers to gas generated by water vapor passing through hot coke, and the main components are carbon monoxide and hydrogen, and possibly contain a small amount of carbon dioxide, nitrogen, methane and other components.
The technical scheme of the invention is as follows:
a recycling method of waste lubricating oil sludge comprises the following steps:
(1) Reacting the waste lubricating oil sludge in a water gas atmosphere, and carrying out solid-liquid separation after the reaction is completed;
(2) And distilling the obtained liquid phase to obtain regenerated lubricating oil base oil, and drying the obtained solid phase product to obtain iron powder particles.
According to the invention, preferably, the water gas in step (1) is prepared in situ from a water gas producer;
or CO and H 2 Is a mixed gas of (a) and (b);
further preferred, CO and H 2 The molar ratio of (2) is between 1:0.01 and 1:100, more preferably between 1:0.5 and 1:10.
According to the invention, the reaction temperature in step (1) is preferably 150 to 370℃and more preferably 200 to 300 ℃.
According to the present invention, the reaction pressure in step (1) is preferably from 0.2 to 5.0MPa, more preferably from 0.5 to 2.0MPa.
According to the invention, the reaction time in step (1) is preferably from 1 to 48 hours, more preferably from 3 to 10 hours.
According to the present invention, it is preferable that the solid-liquid separation operation in step (1) is filtration, centrifugal separation or membrane separation.
According to the present invention, preferably, the distillation in step (2) is reduced pressure distillation;
preferably, the distillation pressure is from 2 to 30kPa.
According to the present invention, it is preferable that the fraction having a boiling point of 500 ℃ or lower is distilled in the step (2) to be used as a base oil for preparing a lubricating oil, and the residue having a boiling point of 500 ℃ or higher is used as a fuel.
According to the present invention, preferably, the drying in step (2) is natural drying or heat drying.
Compared with the prior art, the invention has the following advantages:
1. the invention utilizes the strong interaction of CO and iron phases in the water gas, thereby reducing the separation resistance of the oil phase and the iron phases and realizing the rapid separation of the oil phase and the iron phases.
2. The iron phase obtained by separation in the invention has low oil content, can be directly used as raw materials or catalysts for industrial production, and does not need other pretreatment.
3. Compared with the pure hydrogenation regeneration process, the method has strong interaction between CO and the iron phase, so that the temperature and pressure of the reaction can be greatly reduced, the risk of high-temperature high-pressure reaction is reduced, and the production cost is reduced.
4. Compared with pure hydrogen, the water gas has low cost and low reaction temperature, can further reduce the production cost and improve the profit margin of the regeneration process.
Drawings
Fig. 1 is an X-ray diffraction spectrum of the iron powder particles obtained in example 1.
Fig. 2 shows the effect of the iron powder particles obtained in example 1 on the catalytic degradation of norfloxacin.
Detailed Description
The invention is further explained below by means of specific embodiments in conjunction with the drawings. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The raw materials used in the examples are all conventional raw materials, products are purchased commercially, and the equipment used is conventional equipment.
The waste lubricating sludge described in the examples was taken from a certain mill.
Example 1
The reaction mode of this example is a kettle batch reaction. Adding 1 kg of waste lubricating oil sludge into a reaction kettle, and after leak detection, introducing water gas into the reaction kettle, wherein CO and H 2 The molar ratio is 1:1.25, the partial pressure of water gas is controlled to be 0.5MPa, the gas-oil ratio is 500, and the temperature is raised to the temperature under the stirring conditionThe temperature was kept at 280℃for 8 hours. And after the reaction is cooled naturally, carrying out filter pressing separation on the mixture in the kettle to obtain a liquid oil phase and a solid iron phase. Distilling the oil phase under reduced pressure of 30kPa, collecting fraction with boiling point below 500 deg.C, and obtaining base oil for preparing lubricating oil, wherein residual oil below 500 deg.C can be used as fuel. Drying the solid iron phase at 105 ℃ to obtain the iron powder particles.
Example 2
The reaction mode of this example is a kettle batch reaction. Adding 1 kg of waste lubricating oil sludge into a reaction kettle, and after leak detection, introducing water gas into the reaction kettle, wherein CO and H 2 The molar ratio is 1:0.5, the partial pressure of water gas is controlled to be 0.3MPa, the gas-oil ratio is controlled to be 500, and the temperature is raised to 200 ℃ under the stirring condition, and the temperature is kept for 15 hours. And after the reaction is cooled naturally, centrifugally separating the mixture in the kettle to obtain a liquid oil phase and a solid iron phase. The oil phase is distilled under reduced pressure of 20kPa, and fractions with boiling point below 500 ℃ are collected, so that the base oil for preparing lubricating oil can be obtained, and the residual oil with the boiling point below 500 ℃ can be used as fuel. Drying the solid iron phase at 105 ℃ to obtain the iron powder particles.
Example 3
The reaction mode of this example is a kettle batch reaction. Adding 1 kg of waste lubricating oil sludge into a reaction kettle, and after leak detection, introducing water gas into the reaction kettle, wherein CO and H 2 The molar ratio is 1:3, the partial pressure of water gas is controlled to be 0.8MPa, the gas-oil ratio is 500, and the temperature is raised to 250 ℃ under the stirring condition, and the temperature is kept for 13 hours. And after the reaction is cooled naturally, carrying out suction filtration and separation on the mixture in the kettle to obtain a liquid oil phase and a solid iron phase. The oil phase is distilled under reduced pressure of 25kPa, and fractions with boiling point below 500 ℃ are collected, so that the base oil for preparing lubricating oil can be obtained, and the residual oil with the boiling point below 500 ℃ can be used as fuel. Drying the solid iron phase at 105 ℃ to obtain the iron powder particles.
Example 4
The reaction mode of this example is a kettle batch reaction. Adding 1 kg of waste lubricating oil sludge into a reaction kettle, and after leak detection, introducing water gas into the reaction kettle, wherein CO and H 2 The molar ratio is 1:10, the partial pressure of water gas is controlled to be 1.0MPa, the gas-oil ratio is 500, and the ratio is thatHeating to 300 ℃ under stirring, and preserving heat for 5 hours. And after the reaction is cooled naturally, carrying out filter pressing separation on the mixture in the kettle to obtain a liquid oil phase and a solid iron phase. Distilling the oil phase under reduced pressure of 30kPa, collecting fraction with boiling point below 500 deg.C, and obtaining base oil for preparing lubricating oil, wherein residual oil below 500 deg.C can be used as fuel. Drying the solid iron phase at 105 ℃ to obtain the iron powder particles.
Test example 1
The base oil obtained in example 1 was uniformly mixed with an emulsifier, a lubricant, an anti-rust agent, an antioxidant, etc., to prepare a regenerated rolling oil, and the results of the various index tests are shown in table 1.
TABLE 1 regenerated Rolling oil Performance index
| Kinematic viscosity (mm) 2 /s，40℃) | 8.25 |
| Flash point (. Degree. C.) | 182 |
| Corrosion condition of steel plate | Without any means for |
| Ash (wt%) | Without any means for |
| Tribological Properties (four-ball test, P) B /N) | 473 |
| Acid value (mgKOH/g) | 0.03 |
| Saponification value(mgKOH/g) | 3.9 |
The crystal structure of the obtained iron powder particles was measured by X-ray diffraction, and it can be seen that all diffraction peaks in FIG. 1 correspond to Fe 3 O 4 The characteristic peaks of (2) indicate that the main component of the iron powder particles is Fe 3 O 4 。
Test example 2
The catalytic performance of the obtained iron powder particles in Fenton-like catalytic reaction is examined by an antibiotic norfloxacin degradation experiment. The specific experimental steps are as follows: in a 200ml beaker, iron powder particles are uniformly dispersed in 100ml simulated norfloxacin waste water, the addition amount of the iron powder particles is 0.1mg/L, the norfloxacin concentration is 10mg/L, and the solution pH=5.0. Then, hydrogen peroxide was added to the system to start the reaction, and the amount of hydrogen peroxide added was 30mM. 1.5ml of the reaction solution was taken with a syringe and filtered with a 0.45 μm filter at a preset time interval, and finally 1ml of methanol was added to quench the free radicals, the reaction was terminated, and the concentration of norfloxacin in the solution was measured by high performance liquid chromatography.
Fig. 2 shows the concentration change of norfloxacin during degradation. It can be seen that the degradation of norfloxacin is not significant when only hydrogen peroxide is present in the system. When the iron powder particles obtained in example 1 were added to the system, the norfloxacin was degraded very rapidly, indicating that the obtained iron powder particles could be used directly and had a very good catalytic effect.
Test example 3
The oil content of the iron powder particles obtained in test example 1 was less than 8%. Before treatment, the mass content of the oil phase in the waste lubricating oil mud is more than 30%. Therefore, after the treatment of the invention, the oil content of the solid phase is greatly reduced, and on one hand, the oil phase is well recovered; on the other hand, the iron powder particles have little oil remained, and can be directly used as a raw material for industrial production, such as powder metallurgy, or directly used as a catalyst for catalyzing certain reactions, such as Fenton-like reaction.
Claims (9)
1. A recycling method of waste lubricating oil sludge comprises the following steps:
(1) Reacting the waste lubricating oil sludge in a water gas atmosphere, and carrying out solid-liquid separation after the reaction is completed; the reaction temperature is 150-370 ℃, the reaction pressure is 0.2-1.0 MPa, and CO and H in water gas 2 The molar ratio of (2) is between 1:0.5 and 1:10;
(2) Distilling the obtained liquid phase to obtain regenerated lubricating oil base oil, and drying the obtained solid phase product to obtain iron powder particles; distilling to obtain fraction with boiling point below 500 deg.C as base oil for preparing lubricant, and residue with boiling point above 500 deg.C as fuel; the main component of the iron powder particles is Fe 3 O 4 。
2. The method for recycling waste lubricating oil sludge according to claim 1, wherein the water gas in the step (1) is prepared in situ by a water gas producer, or is CO and H 2 Is a mixed gas of (a) and (b).
3. The method for recycling waste lubricating oil sludge according to claim 1, wherein the reaction temperature in the step (1) is 200-300 ℃.
4. The method for recycling waste lubricating oil sludge according to claim 1, wherein the reaction time in the step (1) is 1 to 48 hours.
5. The method for recycling waste lubricating oil sludge according to claim 4, wherein the reaction time in the step (1) is 3 to 10 hours.
6. The recycling method of waste lubricating oil sludge according to claim 1, wherein the solid-liquid separation operation in the step (1) is filtration or centrifugal separation or membrane separation.
7. The method for recycling waste lubricating oil sludge according to claim 1, wherein the distillation in the step (2) is reduced pressure distillation.
8. The method for recycling waste lubricating sludge according to claim 7, wherein the distillation pressure in the step (2) is 2 to 30kPa.
9. The recycling method of the waste lubricating oil sludge according to claim 1, wherein the drying in the step (2) is natural airing or heating and drying.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1127145A (en) * | 1965-06-23 | 1968-09-11 | Centro Sperimentale Metallurgico Spa | Process of producing pure iron powder and product thereof |
| US3980551A (en) * | 1975-12-18 | 1976-09-14 | Hydrocarbon Research, Inc. | Refining of waste lube oil to prepare usable lubestock |
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