Washing regeneration complexing agent for waste oil adsorbent, preparation method and regeneration method of waste oil adsorbent

Abstract

The invention provides a washing regeneration complexing agent for a waste oil adsorbent, a preparation method and a regeneration method of the waste oil adsorbent, and aims at performing regeneration treatment on an invalid adsorbent after treating waste electric oil to recover the activity of the adsorbent. The washing regeneration complexing agent is prepared by mixing alkali, sodium peroxide, rare earth oxide, an organic solvent and a surfactant; the regeneration method comprises the following steps: putting the invalid adsorbent into the ultrasonic bubbling cleaning device, adding the washing regeneration complexing agent to clean and remove residual oil in the invalid adsorbent and dredge internal pore channels of the adsorbent, then introducing water vapor to effectively remove pollutants such as organic matters remaining in the adsorbent, and finally drying to obtain the regenerated adsorbent. The process flow is simple, the performance of the regenerated adsorbent is greatly improved, the regeneration stability is high, and the cyclic utilization of the waste oil adsorbent is realized.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of adsorption purification and regeneration of power oil, and particularly relates to a washing and regeneration composite agent for waste oil adsorbent, a preparation method and a regeneration method of waste oil adsorbent. BACKGROUND

[0002] Power oil mainly refers to transformer oil, turbine lubricating oil and phosphate ester fire-resistant oil, which mainly plays a role of lubrication, cooling, insulation, arc extinguishing and speed regulation in equipment, and the quality thereof is directly related to the safe and stable operation of power equipment. During the operation of power equipment, the oil product is affected by factors such as temperature, electric field, air, moisture and metal impurities, and thus deteriorates to generate a large amount of organic, salt and colored impurities, which leads to a substantial decrease in the performance of the oil in terms of physics, chemistry and electricity, thereby affecting the service life of the oil product, and in severe cases, causing equipment failure, and even causing major accidents such as equipment burning and explosion. The adsorption purification technology has developed into an important power oil purification and regeneration treatment technology due to its simple operation process and easy industrialization and many other advantages. Currently, the commonly used power oil regeneration adsorbent mainly includes white clay, aluminum oxide, silica-alumina gel, molecular sieve and silica gel. However, the regeneration process of the power oil adsorbent is not mature at present, and most manufacturers often discard the used adsorbent after simple treatment, which not only wastes resources but also easily causes secondary pollution to the environment. Therefore, the regeneration of the failed power oil adsorbent to realize the reuse of the adsorbent and prolong the service life of the adsorbent has a very important practical significance in the field of power oil purification and regeneration technology, and has good social and economic benefits. Patent CN112108136A provides a regeneration treatment method of deteriorated waste transformer insulating oil adsorbent, which is used to treat the powder or sludge adsorbent containing oil sludge residues, so that the adsorbent can be regenerated and applied to the adsorption of deteriorated waste transformer insulation. However, the patent is only applicable to the regeneration of XDK series adsorbent, and the range of transformer oil adsorbent covers various porous materials, and the above regeneration method is not universal.

[0003] Patent CN110523404A provides a regeneration method of transformer oil adsorbent, which is repeatedly leached by an organic solvent, washed by acid and alkali for multiple times, and calcined in an inert gas atmosphere to obtain regenerated transformer oil adsorbent with high regeneration performance. However, the patent application involves many steps, is only applicable to the regeneration of transformer oil adsorbent, and is not used for the adsorption and regeneration of turbine lubricating oil and phosphate ester fire-resistant oil, and has a narrow application range. Therefore, the application provides a washing and regeneration composite agent for transformer oil, steam turbine oil and phosphate ester fire-resistant oil adsorbents and a regeneration method thereof, which has simple operation, low cost, ensures efficient regeneration and recycling of the adsorbents and has important significance for environmental protection and resource saving. SUMMARY

[0004] The application provides a washing and regeneration composite agent for waste oil adsorbents, a preparation method and a regeneration method of waste oil adsorbents.

[0005] To achieve the above object, the application adopts the following technical scheme. The washing and regeneration composite agent for waste oil adsorbents is composed of alkali, oxidized rare earth, sodium peroxide, organic solvent, surfactant and water.

[0006] Further, in the washing and regeneration composite agent, the weight percentage of the alkali is 30% to 50%, the weight percentage of the oxidized rare earth is 0.2% to 2%, the weight percentage of the sodium peroxide is 0.5% to 3%, the weight percentage of the organic solvent is 20% to 40%, the weight percentage of the surfactant is 0.5% to 10%, and the rest is water.

[0007] Further, the alkali is sodium hydroxide, potassium hydroxide or sodium carbonate, and preferably sodium hydroxide.

[0008] Further, the oxidized rare earth is lanthanum oxide or cerium oxide.

[0009] Further, the organic solvent is one or a mixture of several of petroleum ether, alcohol and toluene, and preferably petroleum ether, and the boiling point of the petroleum ether is 60 to 90 DEG C.

[0010] Further, the surfactant is alkyl amine ester (purity 98% and above) or triethanolamine.

[0011] The application also provides a preparation method of the washing and regeneration composite agent. The sodium peroxide and sodium hydroxide are mixed with water respectively to obtain a sodium peroxide solution and a sodium hydroxide solution; the oxidized rare earth is added into the sodium peroxide solution and stirred until the oxidized rare earth is completely dissolved, and then mixed with the sodium hydroxide solution to obtain a mixed solution; the organic solvent and the surfactant are added into the mixed solution and stirred uniformly to obtain the washing and regeneration composite agent.

[0012] The application also provides a regeneration method of waste oil adsorbents using the washing and regeneration composite agent. S1, the invalid waste oil adsorbent is placed in an ultrasonic bubble cleaning device, a washing and regeneration composite agent is added, ultrasonic cleaning is carried out, compressed air is sprayed out through the small holes of the bubble tube, high-pressure bubbles are generated, the cleaning liquid in the cleaning tank is in a rolling state, which is beneficial to dredge the internal pores of the adsorbent, and the residual oil in the adsorbent is effectively cleaned; S2, the waste oil adsorbent treated in step S1 is put into a reactor, and water vapor is continuously introduced into the aeration pipe arranged at the bottom of the reactor, the internal pores are cleaned and repaired through the water vapor, so that the organic pollutants in the waste oil adsorbent are removed, and the adsorbent is activated and regenerated; S3, the waste oil adsorbent treated in step S2 is put into an oven for drying, and the waste oil adsorbent with restored activity is obtained.

[0013] Further, in step S1, the ultrasonic cleaning temperature is 40-60 DEG C, and the cleaning time is 60-120 min.

[0014] Further, in step S2, the steam activation temperature is 120-250 DEG C, the pressure is 0.1-0.5 MPa, and the activation time is 100-200 min.

[0015] Further, in step S3, the drying temperature is 120-200 DEG C, and the drying time is 10-20 hours.

[0016] Further, the waste oil adsorbent is alumina, silica alumina gel, molecular sieve or silica gel.

[0017] The beneficial effects of the present application are: (1) The present application adopts a strong oxidizing alkaline system to prepare an active solution, which can effectively destroy and decompose the carbon chain structure in the oil, so that it becomes small molecular substances which are easier to handle, and the oil sludge, colloid and other pollutants in the pores of the adsorbent are oxidized into oligomeric state, which is beneficial to clean and dredge the pores of the adsorbent.

[0018] (2) The rare earth element has strong chemical activity, can promote the reaction rate and effect of the cleaning liquid, enhance the stability and antioxidant properties of the cleaning liquid, prolong the service life of the cleaning liquid, and can improve the oil removal efficiency when compounded with the surfactant. The rare earth molecule has ion exchange effect, so that the oil / carbon molecules are not polymerized, so that the accumulated carbon and metal ion pollutants in the pores of the adsorbent can be cleaned.

[0019] (3) The surface active agent such as alkyl amine ester OTE or triethanolamine of the present application has low surface tension, rich and delicate foam and stability, and can maintain stable performance under different environmental conditions. It is resistant to strong alkali and high temperature, and can maintain excellent performance in a strong alkaline environment, and can improve the removal of oily dirt, especially non-polar sebum. At the same time, by increasing the alkalinity, the decontamination performance can be improved. And it has excellent compatibility, can improve the removal of oily dirt, especially non-polar sebum, and has excellent compatibility.

[0020] (4) The hot steam method applied in the present application is a high-efficiency adsorbent thermal activation method, which places the adsorbent in water vapor for heating, so as to realize cleaning and repair of the internal pores of the adsorbent. At the same time, this method has high selectivity to impurities and organic matter, and can effectively improve the adsorption performance of the adsorbent crystal.

[0021] (5) The sodium peroxide, rare earth oxide and surfactant have a synergistic effect, which improves the treatment performance of the washing and regeneration composite agent. The sodium peroxide can oxidize the rare earth element to a high valence state, and the surfactant can reduce the surface energy of the rare earth oxide, promote its uniform dispersion in the adsorption system, and increase the contact area. The high valence rare earth element obtained by oxidation of sodium peroxide can separate rare earth ions with different valences with the aid of surfactant. And the specific functional groups (such as carboxyl and amine groups) in the surfactant molecules can form complexes with rare earth ions, which helps the oxidation reaction to proceed. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 is a waste oil adsorbent before and after regeneration treatment by the washing and regeneration composite agent of the present application. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical scheme and advantages of the embodiments of the present application more clear, the technical scheme in the embodiments of the present application will be described clearly and completely in combination with the embodiments of the present application and the drawings. Obviously, the described embodiments are part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0024] Embodiment 1 The present embodiment provides a washing and regeneration composite agent for waste oil adsorbent, which is prepared from the following materials in weight percentage: sodium hydroxide 30%, lanthanum oxide 0.2%, sodium peroxide 0.5%, petroleum ether 30%, alkyl amine ester 5% and deionized water 34.3%.

[0025] The preparation method of the washing and regeneration composite agent is as follows: sodium peroxide and sodium hydroxide are respectively mixed with deionized water, and stirred until completely dissolved to obtain a sodium peroxide solution and a sodium hydroxide solution; lanthanum oxide is added to the sodium peroxide solution, stirred at room temperature for 2 hours until the lanthanum oxide is completely dissolved, then mixed with the sodium hydroxide solution to obtain a mixed solution; petroleum ether and alkyl amine ester are added to the mixed solution and stirred uniformly to obtain the washing and regeneration composite agent.

[0026] The method for regenerating the waste oil adsorbent by using the washing and regeneration composite agent comprises the following steps: S1, the waste oil adsorbent (alumina) saturated with adsorption is placed in an ultrasonic washing device, the washing and regeneration composite agent is added, and ultrasonic cleaning is performed at a temperature of 60 DEG C for 100 min, the residual oil in the adsorbent is cleaned by ultrasonic bubbling, and the internal pores of the adsorbent are dredged.

[0027] S2, the waste oil adsorbent (alumina) treated in step S1 is put into a reactor, and water vapor is continuously introduced into the aeration pipe arranged at the bottom of the reactor, the steam activation temperature is 200 DEG C, the pressure is 0.5 MPa, and the activation time is 150 min. The internal pores are cleaned and repaired by water vapor, so as to remove the organic pollutants in the waste oil adsorbent and realize the activation and regeneration of the adsorbent.

[0028] S3, the waste oil adsorbent treated in step S2 is placed in an oven for drying, the drying temperature is 150 DEG C, and the drying time is 16 hours, so as to obtain the waste oil adsorbent with recovered activity.

[0029] Example 2 The washing and regeneration composite agent for the waste oil adsorbent is prepared from the following materials with a weight percentage of: sodium hydroxide 40%, lanthanum oxide 0.5%, sodium peroxide 1%, petroleum ether 40%, alkyl amine ester 10% and deionized water 8.5%.

[0030] The preparation method of the washing and regeneration composite agent is as follows: sodium peroxide and sodium hydroxide are respectively mixed with deionized water, and stirred until completely dissolved to obtain a sodium peroxide solution and a sodium hydroxide solution; lanthanum oxide is added to the sodium peroxide solution, stirred at room temperature for 2 hours until the lanthanum oxide is completely dissolved, then mixed with the sodium hydroxide solution to obtain a mixed solution; petroleum ether and alkyl amine ester are added to the mixed solution and stirred uniformly to obtain the washing and regeneration composite agent.

[0031] The method for regenerating the waste oil adsorbent by using the washing and regeneration composite agent comprises the following steps: S1, the waste oil adsorbent (silicon aluminum colloid) saturated with adsorption is placed in an ultrasonic washing device, a washing and regeneration composite agent is added, ultrasonic cleaning is carried out, the ultrasonic cleaning temperature is 40 DEG C, the cleaning time is 120 min, the residual oil in the adsorbent is cleaned by ultrasonic bubbling, and the internal pore of the adsorbent is dredged.

[0032] S2, the waste oil adsorbent (aluminum oxide) treated in step S1 is put into a reactor, and water vapor is continuously introduced into the aeration pipe arranged at the bottom of the reactor, the steam activation temperature is 150 DEG C, the pressure is 0.4 MPa, and the activation time is 200 min. By water vapor, the internal pores are cleaned and repaired, so as to remove the organic pollutants in the waste oil adsorbent and realize the activation and regeneration of the adsorbent.

[0033] S3, the waste oil adsorbent treated in step S2 is put into an oven for drying, the drying temperature is 120 DEG C, the drying time is 20 hours, and the waste oil adsorbent with recovered activity is obtained.

[0034] Example 3 The present embodiment provides a washing and regeneration composite agent for waste oil adsorbent, which is prepared from the following materials with a weight percentage: potassium hydroxide 50%, cerium oxide 1.5%, sodium peroxide 3%, ethanol 30%, triethanolamine 5% and deionized water 10.5%. The purity of ethanol is 95% or above, and the specification of triethanolamine is a purity of 85% or above.

[0035] The preparation method of the above-mentioned washing and regeneration composite agent is as follows: sodium peroxide and sodium hydroxide are mixed with deionized water respectively, and stirred until completely dissolved to obtain a sodium peroxide solution and a potassium hydroxide solution; cerium oxide is added to the sodium peroxide solution, stirred at room temperature for 3 hours until the cerium oxide is completely dissolved, then mixed with the potassium hydroxide solution to obtain a mixed solution; ethanol and triethanolamine are added to the mixed solution and stirred uniformly to obtain the washing and regeneration composite agent.

[0036] The method for regenerating the waste oil adsorbent by using the above-mentioned washing and regeneration composite agent comprises the following steps: S1, the waste oil adsorbent (molecular sieve) saturated with adsorption is placed in an ultrasonic washing device, a washing and regeneration composite agent is added, ultrasonic cleaning is carried out, the ultrasonic cleaning temperature is 50 DEG C, the cleaning time is 80 min, the residual oil in the adsorbent is cleaned by ultrasonic bubbling, and the internal pore of the adsorbent is dredged.

[0037] S2, the waste oil adsorbent (aluminum oxide) treated in step S1 is put into a reactor, and water vapor is continuously introduced into the aeration pipe arranged at the bottom of the reactor, the steam activation temperature is 250 DEG C, the pressure is 0.2 MPa, and the activation time is 100 min. By water vapor, the internal pores are cleaned and repaired, so as to remove the organic pollutants in the waste oil adsorbent and realize the activation and regeneration of the adsorbent.

[0038] S3, the waste oil adsorbent treated in step S2 is placed in an oven for drying, the drying temperature is 200℃, and the drying time is 10 hours, to obtain the waste oil adsorbent with recovered activity.

[0039] Example 4 The example provides a washing regeneration composite agent for waste oil adsorbent, which is prepared from the following materials in percentage by weight: potassium hydroxide 30%, cerium oxide 0.2%, sodium peroxide 0.5%, toluene 20%, triethanolamine 0.5%, and deionized water 48.8%. The purity of toluene is 99.8%, and the specification of triethanolamine is a purity of 85% or above.

[0040] The preparation method of the washing regeneration composite agent is as follows: sodium peroxide and sodium hydroxide are respectively mixed with deionized water, and stirred until completely dissolved, to obtain a sodium peroxide solution and a potassium hydroxide solution; cerium oxide is added to the sodium peroxide solution, stirred at room temperature for 2 hours until the cerium oxide is completely dissolved, and then mixed with the potassium hydroxide solution to obtain a mixed solution; toluene and triethanolamine are added to the mixed solution and stirred uniformly to obtain the washing regeneration composite agent.

[0041] The method for regenerating the waste oil adsorbent by using the washing regeneration composite agent is as follows: S1, the waste oil adsorbent (silica gel) saturated with adsorption is placed in an ultrasonic washing device, and the washing regeneration composite agent is added for ultrasonic cleaning, the ultrasonic cleaning temperature is 60℃, and the cleaning time is 60min, the residual oil in the adsorbent is cleaned by ultrasonic bubbling, and the internal pores of the adsorbent are dredged.

[0042] S2, the waste oil adsorbent (alumina) treated in step S1 is put into a reactor, and water vapor is continuously introduced into the aeration pipe arranged at the bottom of the reactor, the steam activation temperature is 120℃, the pressure is 0.5MPa, and the activation time is 200min. The internal pores are cleaned and repaired by water vapor, so as to remove the organic pollutants in the waste oil adsorbent and realize the activation and regeneration of the adsorbent.

[0043] S3, the waste oil adsorbent treated in step S2 is placed in an oven for drying, the drying temperature is 180℃, and the drying time is 15 hours, to obtain the waste oil adsorbent with recovered activity.

[0044] Comparative Example 1 Comparative Example 1 provides a washing regeneration composite agent for waste oil adsorbent, which is different from Example 1 in that no rare earth oxide is added. The washing regeneration composite agent is prepared from the following materials in percentage by weight: sodium hydroxide 30%, sodium peroxide 0.5%, petroleum ether 30%, alkyl amine ester 5%, and deionized water 34.5%.

[0045] The preparation method of the washing and regeneration composite agent is as follows: sodium peroxide and sodium hydroxide are respectively mixed with deionized water, and stirred until completely dissolved to obtain a sodium peroxide solution and a sodium hydroxide solution; the lanthanum oxide is added to the sodium peroxide solution, stirred at room temperature for 2 hours until the lanthanum oxide is completely dissolved, then mixed with the sodium hydroxide solution, and stirred uniformly to obtain a mixed solution; the petroleum ether is added to the mixed solution, and stirred uniformly to obtain the washing and regeneration composite agent.

[0046] The waste oil adsorbent is regenerated by using the washing and regeneration composite agent.

[0047] Comparative Example 2 Comparative Example 2 provides a washing and regeneration composite agent for a waste oil adsorbent, which is different from Example 1 in that no surfactant is added. It is prepared from the following materials in weight percentage: sodium hydroxide 30%, sodium peroxide 0.5%, lanthanum oxide 0.2%, petroleum ether 30%, and deionized water 39.3%.

[0048] The preparation method of the washing and regeneration composite agent is as follows: sodium peroxide and sodium hydroxide are respectively mixed with deionized water, and stirred until completely dissolved to obtain a sodium peroxide solution and a sodium hydroxide solution; the lanthanum oxide is added to the sodium peroxide solution, stirred at room temperature for 2 hours until the lanthanum oxide is completely dissolved, then mixed with the sodium hydroxide solution, and stirred uniformly to obtain a mixed solution; the petroleum ether is added to the mixed solution, and stirred uniformly to obtain the washing and regeneration composite agent.

[0049] The waste oil adsorbent is regenerated by using the washing and regeneration composite agent.

[0050] Effect test The performance of the waste oil adsorbents regenerated in Examples 1-4 and Comparative Examples 1-2 is evaluated.

[0051] Detection method: 5 g of the waste oil adsorbents regenerated in Examples 1-4 and Comparative Examples 1-2 is respectively placed in 100 g of waste transformer oil, waste turbine oil and waste fire-resistant oil, and adsorbed for 4 h at 60℃ by using a magnetic heating stirrer to make the adsorbent fully contact with the oil to achieve the best adsorption effect. After adsorption, the oil is filtered out while hot.

[0052] The dielectric loss, volume resistivity and interfacial tension of the transformer oil, the demulsification degree, acid value of the turbine oil and the acid value, resistivity of the fire-resistant oil after adsorption treatment are detected according to GBT14542-2017 "Transformer Oil Maintenance and Management Guide", GB / T 14541-2017 "Mineral Turbine Oil for Power Plants Maintenance and Management Guide" and DL / T 571-2024 "Phosphate Ester Fire-Resistant Oil for Power Plants Operation and Maintenance Guide", respectively, and compared with an equal amount of new adsorbent. The results are shown in Tables 1-3. The test results show that, compared with the comparative examples, the regenerated adsorbent has more excellent performance indicators, and can basically restore to the level of new adsorbent.

[0053] Table 1 - Comparison of the regeneration performance of the waste oil adsorbent after regeneration on the degraded transformer oil

[0054] Table 2 - Comparison of the regeneration performance of the waste oil adsorbent after regeneration on the degraded turbine oil

[0055] Table 3 - Comparison of the regeneration performance of the waste oil adsorbent after regeneration on the degraded anti-combustion oil

[0056] The above are only preferred embodiments of the present application, and the protection scope of the present application is not limited to the above-mentioned embodiments. Any technical solutions falling within the concept of the present application shall fall within the protection scope of the present application. It should be noted that, for ordinary skilled persons in the art, some improvements and refinements without departing from the principles of the present application shall be considered as falling within the protection scope of the present application.

Claims

1. A washing regeneration composite agent for waste oil adsorbent, characterized in that, the washing regeneration composite agent is composed of alkali, rare earth oxide, sodium peroxide, organic solvent, surfactant and water. 2.The washing regeneration composite agent for waste oil adsorbent according to claim 1, characterized in that, in the washing regeneration composite agent, the weight percentage of alkali is 30%-50%, the weight percentage of rare earth oxide is 0.2%-2%, the weight percentage of sodium peroxide is 0.5%-3%, the weight percentage of organic solvent is 20%-40%, the weight percentage of surfactant is 0.5%-10%, and the rest is water. 3.The washing regeneration composite agent for waste oil adsorbent according to claim 1, characterized in that, the alkali is sodium hydroxide, potassium hydroxide or sodium carbonate. 4.The washing regeneration composite agent for waste oil adsorbent according to claim 1, characterized in that, the rare earth oxide is lanthanum oxide or cerium oxide. 5.The washing regeneration composite agent for waste oil adsorbent according to claim 1, characterized in that, the organic solvent is one or a mixture of several of petroleum ether, alcohol and toluene. 6.The washing regeneration composite agent for waste oil adsorbent according to claim 1, characterized in that, the surfactant is alkyl amine ester or triethanolamine.

7. The method of claim 1 to 6, wherein the method is characterized by, including: mixing sodium peroxide and sodium hydroxide with water respectively to obtain sodium peroxide solution and sodium hydroxide solution; adding rare earth oxide into the sodium peroxide solution and stirring until the rare earth oxide is completely dissolved, and then mixing with the sodium hydroxide solution to obtain a mixed solution; adding organic solvent and surfactant into the mixed solution and stirring uniformly to obtain the washing regeneration composite agent.

8. A method for regenerating a waste oil adsorbent, characterized by, including: S1, placing the failed waste oil adsorbent in an ultrasonic bubble cleaning device, adding the washing regeneration composite agent according to any one of claims 1-6, and cleaning the residual oil in the waste oil adsorbent by ultrasonic cleaning to dredge the internal pores of the waste oil adsorbent; S2, putting the waste oil adsorbent treated in step S1 into a reactor, and continuously introducing water vapor into the aeration pipe arranged at the bottom of the reactor to remove organic pollutants in the waste oil adsorbent by water vapor; S3, putting the waste oil adsorbent treated in step S2 into an oven for drying to obtain the waste oil adsorbent with restored activity. 9.The regeneration method of waste oil adsorbent according to claim 8, characterized in that, in step S1, the ultrasonic cleaning temperature is 40-60℃, and the cleaning time is 60-120min; in step S2, the steam activation temperature is 120-250℃, the pressure is 0.1-0.5MPa, and the activation time is 100-200min; in step S3, the drying temperature is 120-200℃, and the drying time is 10-20 hours. 10.The regeneration method of waste oil adsorbent according to claim 8, characterized in that, the waste oil adsorbent is alumina, silica-alumina gel, molecular sieve or silica gel.

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