CN112479518B - Comprehensive treatment process of cold-rolled aged oil sludge - Google Patents
Comprehensive treatment process of cold-rolled aged oil sludge Download PDFInfo
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- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
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Abstract
The invention relates to a comprehensive treatment process of cold-rolled aged oil sludge, which comprises the steps of mixing aged oil sludge with cleaning fluid, realizing dispersion and cleaning under the action of strong external force of ultrasonic and mechanical stirring, and then carrying out centrifugal separation on the obtained mixed solution. Adding a demulsifier into the upper emulsion phase, and demulsifying to respectively obtain recovered lubricating oil and residual wastewater which can be discharged into a sewage treatment system; the mixed solid phase at the lower layer is dried in vacuum and then is mineralized by microwaves to obtain the iron oxide with extremely low organic matter content on the surface, compared with the prior art, the invention has the following characteristics: 1) The recovery rate of the lubricating oil in the final aged oil sludge reaches more than 90%, the content of residual organic matters on the surface of the iron oxide mainly containing ferroferric oxide is less than 0.1%, and the lubricating oil and the iron oxide can be used as raw materials of other production processes, so that the resource utilization of the aged oil sludge is realized; 2) The process flow is simple and efficient, the equipment requirement is low, the investment cost is low, and the industrial production is convenient to carry out.
Description
Technical Field
The invention belongs to the technical field of harmless and resource utilization of hazardous wastes, and particularly relates to a comprehensive treatment process of cold-rolled aged oil sludge.
Background
In the steel cold rolling industry, rolling liquid is widely applied to reduce friction loss in the rolling process and ensure the quality of rolled pieces, but the problem of difficult rolling of oil sludge is also generated. In the using process of the rolling liquid, the rolling liquid cannot be used continuously due to the problems of impurity-wrapped iron powder, putrefaction, deterioration and the like, and then is discharged into a collecting tank, and the heavier part is settled or adsorbed under the action of gravity or magnetic force to form rolling oil sludge, wherein the main components of the rolling oil sludge are water, lubricating oil and iron powder. Rolled sludge has been listed in the national hazardous waste directory (HW 08) (waste code 900-204-08). However, at present, steel enterprises do not have a good treatment method, and some enterprises are forced to select to stack the steel enterprises in factory buildings. At this time, in order to reduce the amount of sludge and facilitate storage and transportation, an enterprise performs thermal dehydration treatment on sludge, thereby generating aged sludge. During this process, the sludge viscosity increases. Under the dual action of high temperature and oxygen, the oxidation degree of the rolling oil adhered to the surface of the iron powder is intensified to generate fatty acid iron salt (iron soap). The carboxyl of the fatty acid can react with the surface of the iron powder to generate fatty acid iron salt (iron soap), so that the oil stain removal difficulty is increased; the long carbon chains of the alkyl at the other end are associated and entangled with each other, so that the aggregation of iron powder particles is promoted, and the aged oil sludge cannot be perfectly dispersed in the cleaning solution like fresh oil sludge. Meanwhile, fatty acid can be converted into colloid and indissolvable substances, and the colloid has an emulsifying effect and increases the demulsification difficulty of an oil sludge system; the latter cannot be effectively removed by washing. Therefore, the aged sludge cannot be simply subjected to harmless treatment by the conventional cleaning process.
Currently available treatment methods for aged sludge are thermal cracking and extraction. Patent CN 108465449A discloses a microwave thermal cracking method for rolled oil sludge, in which cracked oil is obtained under the action of microwave by means of a cracking catalyst, but the aged oil sludge has a complex composition and a limited cracking degree, and the cracked residue may be a mixture of oil and iron powder, and still belongs to dangerous waste. Patent CN 108341570A discloses a method for recovering rolling oil by vacuum distillation and extracting treatment residues, but the process needs a large amount of organic solvent, is easy to cause air pollution, and requires repeated recovery of the solvent, which results in large energy consumption.
The prior art can not well solve the problem of treatment of aged oil sludge, which is a difficult problem of environmental protection treatment of metal processing enterprises, so that the development of a treatment process which is simple and efficient, realizes resource utilization and has no secondary pollution is urgent.
Disclosure of Invention
The invention aims to solve the problems of harmlessness and resource utilization of cold rolling aged oil sludge, and provides a comprehensive treatment process of cold rolling aged oil sludge so as to achieve the effects of resource utilization and no secondary pollution.
The purpose of the invention can be realized by the following technical scheme:
a comprehensive treatment process of cold-rolled aged oil sludge specifically comprises the following steps:
(A) Mixing the aged oil sludge with a cleaning solution, cleaning in an ultrasonic environment, and simultaneously performing mechanical stirring;
(B) Centrifugally separating the mixed solution obtained in the step (A) to respectively obtain an upper emulsion phase and a lower mixed solid phase;
(C) Adding a demulsifier into the upper emulsion phase obtained in the step (B), stirring, standing for layering to respectively obtain upper recovered lubricating oil and lower wastewater, and discharging the wastewater into a sewage treatment system for further treatment;
(D) Drying the lower mixed solid phase obtained in the step (B) to remove moisture, carrying out microwave mineralization in the air atmosphere,
removing residual organic matters remained on the surface of the iron powder to obtain the iron oxide with extremely low surface organic matter content.
Further, the cleaning solution in the step (A) is composed of water, a surfactant and a dispersion aid, wherein the addition amount of the surfactant is 5-10 wt% of the total mass of the aged oil sludge, and the addition amount of the dispersion aid is 5-15 wt% of the total mass of the aged oil sludge.
Further, the surfactant in the step (A) is one or more of alkylolamide, alkyl glycoside, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkylolamide polyoxyethylene ether or fatty acid polyoxyethylene ester; the auxiliary dispersant is one or more of ethanol, n-butanol, sodium carbonate, sodium silicate, disodium hydrogen phosphate or disodium ethylene diamine tetraacetate. When the concentration of the surfactant reaches or exceeds the critical micelle concentration, the oil stains wrapping the surface of the iron powder can be emulsified and separated from the surface of the iron powder.
Further, the ultrasonic power in the step (A) is 500-1000W, the frequency is 15-25 KHz, preferably 20KHz, and the processing time is 30-60 min. Cavitation bubbles are generated by the transmission of ultrasonic waves in water, the micro jet formed during the fracture is helpful to open the association entanglement among the long carbon chains of the aged oil sludge adhered to the iron powder and promote the dispersion of iron powder particles, wherein the ultrasonic power and frequency have important influence on the cleaning operation of the aged oil sludge. If the ultrasonic power is low and the frequency is low, the generated micro-jet effect is not enough to open the entanglement of the long carbon chains, and the iron powder dispersing effect is not obvious. However, if the ultrasonic power is too high and the frequency is too high, a large amount of generated cavitation bubbles can weaken the transmission of sound waves; meanwhile, a strong cavitation environment formed by excessive microjet action leads the system to tend to be disordered, increases the collision chance of the iron powder and the separated oil stain, and leads the oil stain to be adhered to the surface of the iron powder again; third, too high power and frequency can increase energy consumption and shorten the life cycle of the ultrasound device.
Further, the mechanical stirring speed in the step (A) is 400-700 r/min. Because the viscosity and viscosity of the aged oil sludge are high, perfect dispersion of the oil sludge cannot be realized by simply relying on ultrasound, mechanical stirring which is a strong external force action must be applied to assist the dispersion, the contact of the oil sludge and a cleaning agent is promoted, and the cleaning operation is completed.
Further, the centrifugal rotating speed in the step (B) is 2000-4000 r/min, and the time is 20-50 min.
Further, the addition amount of the demulsifier in the step (C) is 0.1-0.5 wt% of the total mass of the emulsion phase. The demulsifier can effectively reduce the interfacial tension and the interfacial film strength of emulsified water drops, so that oil in the internal phase of emulsion particles breaks through the interfacial film and enters the external phase, oil-water separation occurs, and the emulsified lubricating oil in the step (A) is recovered. The addition amount of the demulsifier has important influence on demulsification operation. If the addition amount of the demulsifier is low, the demulsification effect is not obvious; however, if the amount of the demulsifier is excessively increased, a more stable emulsification system is formed.
Further, the demulsifier in step (C) is one or more of DRC 168, DRI9030 or RTC 330, specifically DRC 168 from aksounbell, DRI9030 from aksounbell or RTC 330 from noreon chemicals.
Further, the drying in the step (D) is vacuum drying, the temperature is 50-90 ℃, the vacuum degree is 0.04-0.07 MPa, preferably 0.05MPa, and the time is 2-10 h. In the iron powder drying process, the iron powder can be effectively prevented from being oxidized by keeping a certain vacuum degree, and the drying speed is increased by greatly reducing the resistance of steam airflow, so that the vacuum degree has important influence on the drying operation of the iron powder. If the vacuum degree is lower, the drying speed is not obviously improved; however, if the vacuum degree is too high, the heat transfer of the system is weakened due to lack of intermediate media, and the heated effect of the iron powder is limited on the contrary; meanwhile, the energy consumption is increased due to the excessively high vacuum degree, and higher requirements are put forward on the aspects of materials, cost and the like of drying equipment.
Further, the microwave power in the step (D) is 300-600W, the frequency is 2200-2500 MHz, preferably 2450MHz, and the treatment time is 10-20 min. The microwave heating is a field heating mode formed by using an electromagnetic field, iron powder is used as a dielectric material, and can be selectively heated into a high-temperature 'hot spot' due to electromagnetic field energy loss generated in microwave radiation, organic matters existing around the 'hot spot' can be finally mineralized into carbon dioxide in an air atmosphere, and therefore microwave power and frequency have important influence on the operation of removing residual organic matters on the surface of the iron powder. If the microwave power is low and the frequency is low, the temperature rise rate of the iron powder is low, the end point temperature is low, and the residual organic matter removal effect is not obvious; however, if the microwave power is too high and the frequency is too high, the temperature rising rate is too high, a temperature runaway phenomenon is easily caused, and the energy consumption is increased due to the too high power and frequency.
The reaction mechanism of the invention is specifically as follows:
compared with fresh oil sludge, the aged oil sludge is more complex in composition, the cleaning treatment of the aged oil sludge cannot be realized only by the traditional cleaning process, and other processes such as ultrasonic and microwave are combined.
The first step of the process is to mix the aged oil sludge with the cleaning fluid and mechanically stir the mixture in an ultrasonic environment. When the concentration of the surfactant in the cleaning solution reaches or exceeds the critical micelle concentration, the surfactant can emulsify the oil stains wrapping the surface of the iron powder and separate the oil stains from the surface of the iron powder. Meanwhile, cavitation bubbles can be generated by ultrasonic wave transmission in water, and micro-jet flow formed during breakage is helpful for opening association entanglement among long carbon chains of aged oil sludge and oil stains and promoting dispersion of iron powder particles. Moreover, the cavitation bubbles are broken to generate local high temperature and high pressure, water molecules in the extreme environment are split to form hydroxyl radicals with strong oxidizing property, and the hydroxyl radicals and oil stains are subjected to oxidation reaction, so that carbon chains of the hydroxyl radicals are broken and converted into organic matters with smaller molecular weight, and the cleaning effect is improved.
And (4) centrifugally separating the mixed solution after cleaning to respectively obtain an emulsion phase and a mixed solid phase. Adding a demulsifier into the emulsified liquid phase to release emulsified lubricating oil, realizing recycling, and discharging residual wastewater into a sewage treatment system; the mixed solid phase obtained by centrifugation is mainly iron powder and insoluble matters in aged oil sludge, and partial oil stains still remain on the surface of the iron powder. After vacuum drying, the mixed solid phase is placed in a microwave generator, iron powder radiated by microwaves is selectively heated into a high-temperature hot spot due to the loss of electromagnetic field energy, organic matters existing around the hot spot are finally mineralized into carbon dioxide under the air atmosphere, and the iron powder is oxidized into iron oxides such as ferroferric oxide, ferrous oxide and the like, so that recycling is realized.
Compared with the prior art, the invention has the following advantages:
1) The recovery rate of the lubricating oil in the final aged oil sludge reaches more than 90%, the content of the residual organic matters on the surface of the iron oxide is less than 0.1%, and the lubricating oil and the iron oxide can be used as raw materials of other production processes, so that the resource utilization of the aged oil sludge is realized;
2) The process flow is simple and efficient, the equipment requirement is low, the investment cost is low, and the industrial production is easy to carry out.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is an XRD analysis of the solid obtained after microwave mineralization.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
In order to solve the technical problems of harmlessness and resource utilization of the cold-rolled aged oil sludge, the applicant has conducted extensive and intensive research and provides a comprehensive treatment process of the cold-rolled aged oil sludge, so as to achieve the effects of resource utilization and no secondary pollution.
The comprehensive treatment process of the cold-rolled aged oil sludge specifically comprises the following steps, and fig. 1 is a process flow chart of the invention:
(A) Mixing the aged oil sludge with a cleaning solution, and mechanically stirring in an ultrasonic environment to obtain a mixed solution;
(B) Centrifugally separating the mixed solution obtained in the step (A) to respectively obtain an upper emulsion phase and a lower mixed solid phase;
(C) Adding a demulsifier into the upper emulsion phase obtained in the step (B), stirring, standing and layering to respectively obtain upper recovered lubricating oil and lower wastewater, and discharging the wastewater into a sewage treatment system for further treatment;
(D) And (C) drying the lower mixed solid phase obtained in the step (B) to remove moisture, carrying out microwave mineralization in the air atmosphere, and removing residual organic matters remained on the surface of the iron powder to obtain the iron oxide with extremely low surface organic matter content.
As an embodiment, the cleaning solution in the step (a) is composed of water, a surfactant and a dispersion aid, wherein the addition amount of the surfactant is 5wt.% to 10wt.% of the total mass of the aged oil sludge; the addition amount of the dispersion aid is 5-15 wt% of the total mass of the aged oil sludge. Wherein the surfactant is one or more of alkylolamide, alkyl glycoside, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene, alkylolamide polyoxyethylene ether or fatty acid polyoxyethylene ester; the auxiliary dispersant is one or more of ethanol, n-butanol, sodium carbonate, sodium silicate, disodium hydrogen phosphate or disodium ethylene diamine tetraacetate.
As an embodiment, the ultrasonic power of step (A) is 500-1000W, the frequency is 15-25 KHz, more preferably 20KHz, and the cleaning time is 30-60 min.
As an embodiment, the mechanical stirring speed of the step (A) is 400-700 r/min.
As an embodiment, the centrifugal speed of the step (B) is 2000-4000 r/min, and the time is 20-50 min.
As an embodiment, the demulsifier of step (C) is added in an amount of 0.1wt.% to 0.5wt.% of the total mass of the emulsion phase, and the demulsifier is a mixture of one or more of DRC 168 by aksunobel, DRI9030 by aksunobel, or RTC 330 by noreon chemicals, ltd.
In one embodiment, the drying in step (D) is vacuum drying at a temperature of 50 to 90 ℃ under a vacuum of 0.04 to 0.07MPa, more preferably 0.05MPa, for a period of 2 to 10 hours.
As an embodiment, the microwave power in step (D) is 300-600W, the frequency is 2200-2500 MHz, more preferably 2450MHz, and the treatment time is 10-20 min.
The present invention will be fully described with reference to the following specific examples.
Example 1
The concrete embodiment of the invention is illustrated by taking aged oil sludge of a certain cold-rolling steel mill in Zhejiang as an example.
The oil sludge was a black viscous oil having a water content of about 5%, a solids content of about 32%, an oil content of about 63%, a saponification value of 124mg KOH/g, and a viscosity of 43.2 pas (60 ℃ C.).
Mixing 100 parts of the oil sludge with 500 parts of water, selecting 1 part of alkylolamide, 2 parts of fatty alcohol-polyoxyethylene ether and 2 parts of fatty acid-polyoxyethylene ester as a surfactant, selecting 1 part of ethanol, 3 parts of sodium silicate and 1 part of disodium ethylene diamine tetraacetate as an auxiliary dispersing agent, wherein the ultrasonic power is 500W, the frequency is 25KHz, the mechanical stirring speed is 400r/min, and the cleaning time is 60min. And (4) performing centrifugal separation on the black mixed liquid after the cleaning is finished, wherein the rotating speed is 2000r/min, and the time is 50min. Adding 1 part of DRC 168 and 1 part of RTC 330 into the upper emulsion phase after the centrifugation is finished, stirring, standing and layering, wherein the upper layer is recovered lubricating oil, the mass of the recovered lubricating oil accounts for more than 90% of the oil content of the aged oil sludge, the saponification value is 132mg KOH/g, the water phase is discharged into a sewage treatment system, and the COD is Cr About 1500mg/L. And (3) carrying out vacuum drying on the centrifuged mixed solid phase at the temperature of 50 ℃ under the vacuum degree of 0.07MPa for 8 hours. After drying, the mixture enters a microwave generating device, the microwave power is 600W, the frequency is 2450MHz, the mixture is treated for 10min in an air atmosphere, and the organic matter content of the solid residue is increased after the microwave dryingThe amount is less than 0.1%, and an XRD analysis spectrum in figure 2 shows that iron oxide obtained by microwaves is ferroferric oxide and ferrous oxide, wherein the ferroferric oxide accounts for 88.63 wt%, and the ferrous oxide accounts for 11.37 wt%, so that the iron oxide can be used as a wave absorbing material or an iron catalyst to be recycled.
Example 2
The aged oil sludge of a certain steel plant in the sea is taken as an example to illustrate the specific embodiment of the invention.
The oil sludge can be piled up in a factory for more than one year, the water content is about 9 percent, the solid content is about 16 percent, the oil content is about 75 percent, the saponification value is 132mg KOH/g, and the viscosity is 36.5 pas (60 ℃).
Mixing 100 parts of the aged oil sludge with 500 parts of water, selecting 2 parts of alkyl glycoside, 2 parts of alkylphenol polyoxyethylene and 3 parts of alkylolamide polyoxyethylene ether as a surfactant, selecting 1 part of n-butyl alcohol and 14 parts of sodium silicate as an auxiliary dispersant, wherein the ultrasonic power is 1000W, the frequency is 20KHz, the mechanical stirring speed is 400r/min, and the cleaning time is 30min. And (4) centrifugally separating the black mixed liquid after the cleaning is finished, wherein the rotating speed is 4000r/min, and the time is 20min. Adding 1 part of DRI9030 and 2 parts of RTC 330 into the upper-layer emulsion after the centrifugation is finished, stirring, standing and layering to obtain an upper-layer recovered lubricating oil with the mass accounting for more than 90% of the oil content of the aged oil sludge and the saponification value of 139mg KOH/g, discharging the water phase into a sewage treatment system, and adding COD (chemical oxygen demand) into the upper-layer recovered lubricating oil Cr About 2170mg/L. And (3) taking the centrifuged mixed solid phase, and drying in vacuum at 90 ℃ under the vacuum degree of 0.04MPa for 2h. And after drying is finished, putting the mixture into a microwave generating device, treating the mixture for 20min in an air atmosphere with the microwave power of 300W and the frequency of 2200MHz, and enabling the content of residual organic matters in the iron oxide to be less than 0.1% after the microwave is finished.
Example 3
The concrete embodiment of the invention is illustrated by taking the aged oil sludge of a certain cold-rolled steel mill in Jiangsu as an example.
The oil sludge had a water content of about 13%, a solids content of about 31%, an oil content of about 56%, a saponification value of 113mg KOH/g and a viscosity of 27.4 pas (60 ℃ C.).
Mixing 100 parts of the aged oil sludge with 500 parts of water, wherein 2 parts of alkyl glycoside, 4 parts of fatty alcohol-polyoxyethylene ether and 4 parts of alkylphenol polyoxyethylene are selected as a surfactantVinyl ether and an auxiliary dispersing agent are selected from 1 part of ethanol, 3 parts of disodium ethylene diamine tetraacetate and 5 parts of sodium carbonate, the ultrasonic power is 800W, the frequency is 15KHz, the mechanical stirring speed is 550r/min, and the cleaning time is 40min. And (4) centrifugally separating the black mixed liquor after the cleaning is finished, wherein the rotating speed is 3500r/min, and the time is 40min. Adding 1 part of DRC 168 into the upper emulsion phase after the centrifugation is finished, stirring, standing and layering, wherein the upper layer is recovered lubricating oil, the mass of the recovered lubricating oil accounts for more than 90% of the oil content of the aged oil sludge, the saponification value is 120mg KOH/g, the water phase is discharged into a sewage treatment system, and the COD is Cr About 4400mg/L. And (3) carrying out vacuum drying on the centrifuged mixed solid phase at the temperature of 90 ℃ under the vacuum degree of 0.05MPa for 4 hours. And after drying, putting the mixture into a microwave generating device, treating the mixture for 15min in an air atmosphere with the microwave power of 600W and the frequency of 2450MHz, wherein the content of residual organic matters in the iron oxide is less than 0.1% after the microwave is finished.
Example 4
The concrete embodiment of the invention is illustrated by taking aged oil sludge of certain cold-rolled steel mill in Hebei as an example.
The oil-sludge water content was about 5%, the solid content was about 25%, the oil content was about 70%, the saponification value was 128mg KOH/g, and the viscosity was 50.1 pas (60 ℃ C.).
Mixing 100 parts of the aged oil sludge with 500 parts of water, selecting 2 parts of alkyl glycoside and 4 parts of fatty alcohol-polyoxyethylene ether as a surfactant, selecting 1 part of n-butyl alcohol and 9 parts of sodium silicate as an auxiliary dispersing agent, wherein the ultrasonic power is 1000W, the frequency is 20KHz, the mechanical stirring speed is 700r/min, and the cleaning time is 50min. And (4) centrifugally separating the black mixed liquid after the cleaning is finished at the rotating speed of 4000r/min for 50min. Adding 1 part of DRC 168 and 3 parts of RTC 330 into the upper emulsion phase after the centrifugation is finished, stirring, standing and layering, wherein the upper layer is recovered lubricating oil, the mass of the recovered lubricating oil accounts for more than 90% of the oil content of the aged oil sludge, the saponification value is 130mg KOH/g, the water phase is discharged into a sewage treatment system, and the COD is Cr About 1920mg/L. And (3) carrying out vacuum drying on the centrifuged mixed solid phase at the temperature of 70 ℃ under the vacuum degree of 0.06MPa for 7h. And after drying is finished, putting the mixture into a microwave generating device, treating the mixture for 10min in an air atmosphere with the microwave power of 600W and the frequency of 2500MHz, wherein the content of residual organic matters in the iron oxide is less than 0.1% after the microwave is finished.
Example 5
The concrete embodiment of the invention is illustrated by taking aged oil sludge of certain cold-rolling steel mill in Hubei as an example.
The oil-mud water content was about 3%, the solid content was about 39%, the oil content was about 58%, the saponification value was 104mg KOH/g, and the viscosity was 55.4 pas (60 ℃ C.).
Mixing 100 parts of the aged oil sludge with 500 parts of water, selecting 1 part of alkylolamide and 4 parts of alkylphenol polyoxyethylene as a surfactant, selecting 1 part of n-butyl alcohol as an auxiliary dispersant, 3 parts of disodium ethylene diamine tetraacetate and 5 parts of sodium dihydrogen phosphate, wherein the ultrasonic power is 500W, the frequency is 20KHz, the mechanical stirring speed is 700r/min, and the cleaning time is 60min. And (4) centrifugally separating the black mixed liquid after the cleaning is finished, wherein the rotating speed is 4000r/min, and the time is 30min. Adding 1 part of DRC 168 and 2 parts of RTC 330 into the upper layer emulsion after the centrifugation is finished, stirring, standing and layering, wherein the upper layer is recovered lubricating oil, the mass of the recovered lubricating oil accounts for more than 90% of the oil content of the aged oil sludge, the saponification value is 120mg KOH/g, the water phase is discharged into a sewage treatment system, and the COD is Cr About 2270mg/L. And (3) carrying out vacuum drying on the centrifuged mixed solid phase at the temperature of 90 ℃ under the vacuum degree of 0.05MPa for 6 hours. And after drying, putting the mixture into a microwave generating device, treating the mixture for 15min in an air atmosphere with the microwave power of 600W and the frequency of 2450MHz, wherein the content of residual organic matters in the iron oxide is less than 0.1% after the microwave is finished.
To show the effect of the process steps of the invention on the results, the invention also carried out the following comparative examples.
Comparative example 1
Taking the example 5 as a reference, the cleaning process of the aged oil sludge is only carried out with ultrasonic treatment and no mechanical stirring, and the rest process steps are the same as those of the example 5, so that most of the aged oil sludge still presents a cluster shape after the cleaning is finished, meanwhile, the mass of the recovered lubricating oil accounts for 25% of the oil content of the aged oil sludge, and the content of the residual organic matters of the iron oxide after the microwave is finished is 9.1%.
Comparative example 2
With reference to example 5, the aged sludge was cleaned without ultrasonic treatment, and only with mechanical agitation, and the remaining process steps were the same as in example 5, resulting in a recovered lubricating oil mass of 67% of the oil content of the aged sludge, and a residual organic matter content of 4.2% of iron oxide after completion of the microwave treatment.
Two comparative examples show that the sonication + mechanical agitation step has a significant impact on the treatment of aged sludge.
Comparative example 3
By taking the example 5 as a reference, the ultrasonic power of the aged oil sludge cleaning process is 200W, the frequency is 10KHz, and the rest process steps are the same as those of the example 5, so that the mass of the recovered lubricating oil accounts for 70% of the oil content of the aged oil sludge, and the content of the residual organic matters in the iron oxide after the microwave is finished is 3.8%.
This indicates that sonication with too little power and too low frequency is detrimental to the treatment of aged sludge.
Comparative example 4
By taking the example 5 as a reference, in the aging sludge cleaning process, the ultrasonic power is 1500W, the frequency is 30KHz, and the rest process steps are the same as those in the example 5, so that the mass of the recovered lubricating oil accounts for 74% of the oil content of the aging sludge, and the content of the residual organic matters of the iron oxide after the microwave treatment is 3.3%.
This indicates that ultra-high power and frequency sonication is detrimental to the treatment of aged sludge.
Comparative example 5
With reference to example 5, in the aging oil sludge treatment process, the demulsifier is not added, only the upper emulsion is subjected to standing operation, and the rest process steps are the same as those in example 5, so that the mass of the recovered lubricating oil accounts for 5% of the oil content of the aging oil sludge, and the water phase CODcr after demulsification exceeds 10 5 mg/L。
This indicates that the addition of demulsifiers is of great importance for the recovery of lubricating oils.
Comparative example 6
By taking the example 5 as a reference, in the aging oil sludge treatment process, the addition amount of the demulsifier is 0.05wt.%, and the rest process steps are the same as those in the example 5, so that the mass of the recovered lubricating oil accounts for 40% of the oil content of the aging oil sludge, and the water phase CODcr after demulsification exceeds 10 5 mg/L。
This indicates that too low an amount of demulsifier added is detrimental to the recovery of lubricating oil.
Comparative example 7
With reference to example 5, in the aged oil sludge treatment process, the addition amount of the demulsifier is 1.0wt.%, and the remaining process steps are the same as those in example 5, so that the mass of the recovered lubricating oil accounts for 80% of the oil content of the aged oil sludge, and the water phase CODcr after demulsification is about 12000mg/L.
This indicates that too high an amount of demulsifier is disadvantageous for the recovery of lubricating oil.
Comparative example 8
With reference to example 5, the aged sludge treatment process was dried in an air atmosphere, and the remaining process steps were the same as in example 5, and as a result, the iron oxide after microwave mineralization was mainly ferric oxide, and thus it was not possible to produce ferroferric oxide with higher economic value, and the content of residual organic matter in the iron oxide was 0.9%.
The vacuum drying is significant for the generation of iron oxide mainly containing ferroferric oxide.
Comparative example 9
The aging sludge treatment process is carried out under the condition that the drying vacuum degree is 0.10MPa by taking the embodiment 5 as a reference, the rest process steps are the same as the embodiment 5, and the time required for completely drying the solid is prolonged to 10 hours.
This indicates that too high a vacuum is detrimental to the rapid drying of the solid after centrifugation.
Comparative example 10
With reference to example 5, the aged sludge treatment process was carried out without microwave mineralization, and the remaining process steps were the same as in example 5, resulting in a recovered lubricating oil mass of 90% of the oil content of the aged sludge and a solid residual organic content of 9.1% after drying.
This indicates that microwave mineralization has a significant effect on the removal of residual organics of iron oxides.
Comparative example 11
With reference to example 5, the aging sludge treatment process was carried out at a microwave power of 50W and a frequency of 900MHz, and the remaining process steps were the same as in example 5, resulting in a residual organic content of 6.1% of iron oxide after microwave mineralization.
This indicates that too little microwave power and too low frequency are detrimental to the removal of residual organics of iron oxide.
Comparative example 12
Referring to example 5, the aged sludge treatment process was carried out at a microwave power of 800W and a frequency of 3000MHz, and the rest process steps were the same as those in example 5, so that the quartz reaction vessel was damaged 2min after the start of the microwave mineralization test, which indicated that the temperature of the system had risen to over 1000 ℃, the iron powder discharge phenomenon was severe, and the test was stopped, at which time the content of residual organic matters in iron oxide was 1.2%.
This indicates that too high microwave power and too low frequency are detrimental to the removal of residual organics of iron oxide.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (11)
1. The comprehensive treatment process of the cold-rolled aged oil sludge is characterized by comprising the following steps:
(A) Mixing the aged oil sludge with a cleaning solution, and mechanically stirring in an ultrasonic environment to obtain a mixed solution; the power of the ultrasonic is 500-1000W, the frequency is 15-25 KHz, and the processing time is 30-60 min;
(B) Centrifugally separating the mixed solution obtained in the step (A) to respectively obtain an upper emulsion phase and a lower mixed solid phase;
(C) Adding a demulsifier into the upper emulsion phase obtained in the step (B), stirring, standing for layering to respectively obtain upper recovered lubricating oil and lower wastewater, and discharging the wastewater into a sewage treatment system for further treatment; the addition amount of the demulsifier is 0.1-0.5 wt.% of the total mass of the upper emulsion phase;
(D) And (B) drying the lower mixed solid phase obtained in the step (B) to remove moisture, carrying out microwave mineralization in the air atmosphere, and removing residual organic matters remained on the surface of the iron powder to obtain the iron oxide with extremely low surface organic matter content.
2. The integrated treatment process of the cold-rolled aged oil sludge as claimed in claim 1, wherein the cleaning solution in the step (A) is composed of water, surfactant and dispersion aid, wherein the addition amount of the surfactant is 5wt.% to 10wt.% of the total mass of the aged oil sludge; the addition amount of the dispersion aid is 5-15 wt% of the total mass of the aged oil sludge.
3. The comprehensive treatment process of the cold-rolled aged oil sludge as claimed in claim 2, wherein the surfactant in the step (A) is one or more of alkylolamide, alkyl glycoside, fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylate, alkylolamide ethoxylate or fatty acid polyoxyethylene ester; the auxiliary dispersant is one or more of ethanol, n-butanol, sodium carbonate, sodium silicate, disodium hydrogen phosphate or disodium ethylene diamine tetraacetate.
4. The integrated treatment process of cold-rolled aged oil sludge according to claim 1, wherein the frequency of the ultrasound in the step (A) is 20 KHz.
5. The comprehensive treatment process of cold-rolled aged oil sludge as claimed in claim 1, wherein the rotation speed of the mechanical stirring in the step (A) is 400-700 r/min.
6. The comprehensive treatment process of the cold-rolled aged oil sludge as claimed in claim 1, wherein the rotation speed of the centrifugation in the step (B) is 2000-4000 r/min, and the treatment time is 20-50 min.
7. The integrated treatment process of cold rolled aged oil sludge according to claim 1, wherein the demulsifier of step (C) is one or more of DRC 168, DRI9030 or RTC 330.
8. The comprehensive treatment process of cold-rolled aged oil sludge as claimed in claim 1, wherein the drying in the step (D) is vacuum drying, the temperature is 50 to 90 ℃, the vacuum degree is 0.04 to 0.07MPa, and the time is 2 to 10 hours.
9. The integrated process for treating cold-rolled aged oil sludge according to claim 8, wherein the vacuum degree in the step (D) is 0.05 MPa.
10. The comprehensive treatment process of cold-rolled aged oil sludge as claimed in claim 1, wherein the microwave in the step (D) has a power of 300 to 600W, a frequency of 2200 to 2500MHz, and a treatment time of 10 to 20min.
11. The integrated treatment process of cold rolling aged oil sludge according to claim 1, wherein the frequency of the microwave in the step (D) is 2450 MHz.
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