Waste oil recovery treatment method for BIPB solvent-free process
By using methods such as water extraction and inorganic salt salting treatment in the BIPB solvent-free production process, efficient recycling and purification of TBHP and BIPB was successfully achieved, solving the problem of waste oil treatment, reducing costs and simplifying the process.
Patent Information
- Application Number
- CN202510234512.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-28
- Publication Date
- 2025-06-03
AI Technical Summary
The waste oil produced by the BIPB solvent-free production process contains a large amount of organic peroxides, which is difficult to deal with and recover. The prior art uses palladium catalysts and a high-cost hydrogen supply system, which is costly and difficult to achieve large-scale promotion.
Using water as the extraction agent, TBHP and BIPB in the waste oil were initially separated, and TBHP and BIPB were extracted and separated by inorganic salt salting treatment and oily extraction agent extraction and separation, and TBHP and BIPB were purified respectively to obtain high-purity products.
It realizes efficient recycling and purification of BIPB and TBHP, reduces processing costs, simplifies process flow, and is easy to promote and apply on a large scale.
Smart Images
Figure CN120081773A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of BIPB production, and specifically to a method for recycling and treating waste oil in the BIPB solvent-free process. Background Art
[0002] The new solvent-free production process of BIPB will generate a large amount of waste oil. The waste oil from the new process contains a large amount of organic peroxides and belongs to waste liquid that is difficult to treat and degrade. Its components include BIPB (1,4-bis(tert-butylperoxy) isopropylbenzene), TBHP (tert-butyl hydroperoxide) and other impurities. The main useful components that can be recycled are BIPB and TBHP. If these waste oils are directly treated, the cost is high and it is a waste. If certain useful components in the process waste oil can be recycled and reprocessed, a large amount of cost can be saved. Chinese Patent Application (Publication No. CN 118791378A) discloses a method for hydrogenating high-purity dimer acid, which mainly hydrogenates the organic matter in the waste oil under solvent-free conditions by using palladium catalyst supported on activated carbon, reduces peroxides and removes acidic groups. However, the palladium catalyst has a high cost, requires a supporting hydrogen supply system, and has high requirements for the pressure resistance of the equipment, so it cannot be widely promoted and applied on a large scale. Summary of the Invention
[0003] In order to solve the above problems, the present invention provides a method for recycling and treating waste oil in the BIPB solvent-free process. The method is simple to operate, can not only convert it into easily treatable wastewater, but also recycle useful components such as BIPB and TBHP in the waste oil to obtain a BIPB product with a relatively high content, which is easy to be widely promoted and applied on a large scale.
[0004] The present invention provides a method for recycling and treating waste oil in the BIPB solvent-free process, which at least includes the following steps: the waste oil is extracted with an extractant and then allowed to stand for stratification to obtain a TBHP wastewater phase and a BIPB waste oil phase; inorganic salts are added to the TBHP wastewater phase for salting-out treatment to obtain crude TBHP and waste brine; the waste brine is recycled; the crude TBHP is purified to obtain pure TBHP; the BIPB waste oil phase is subjected to extraction and separation to obtain crude BIPB; the crude BIPB is refined to obtain pure BIPB.
[0005] In the present invention, the waste oil is derived from the BIPB solvent-free production process, and its components include BIPB, TBHP and impurities.
[0006] As a preferred technical solution, the extractant is selected from at least one of water, methanol, ethanol or acetonitrile, and preferably water.
[0007] As a preferred technical solution, the mass ratio of the waste oil to the extractant is 1:(3-10), and preferably 1:(3-6).
[0008] As a preferred technical solution, the temperature of the extraction is 15-35°C and the time is 20-60 min.
[0009] When performing the extraction of TBHP in the present invention, some organic extractants or compound extractants with high polarity matching degree were tried to ensure the extraction effect. However, it was found in actual operation that the introduction of organic extractants made the obtained TBHP wastewater phase contain BIPB and some organic impurities, which affected the salting-out and recovery content of TBHP and also caused the recovery loss of BIPB in the waste oil. Therefore, by using water as the extractant, the above problems can be avoided while effectively extracting TBHP from the waste oil.
[0010] As a preferred technical solution, the inorganic salt is selected from at least one of anhydrous sodium sulfate, sodium chloride, magnesium sulfate or sodium phosphate, and preferably anhydrous sodium sulfate.
[0011] As a preferred technical solution, the addition amount of the inorganic salt is 20-50% of the mass of the TBHP wastewater phase, and preferably 20-40%.
[0012] As a preferred technical solution, the temperature of the salting-out treatment is 15-35°C and the time is 15-60 min.
[0013] As a preferred technical solution, the purification method is filtration, and the impurities after filtration enter the wastewater tank for treatment.
[0014] As a preferred technical solution, the pure TBHP is condensed with DC to obtain the crude BIPB.
[0015] As a preferred technical solution, the recycling of the waste brine includes: obtaining inorganic salt and aqueous phase by cooling crystallization of the waste brine, the inorganic salt is reused for the salting-out treatment, and the aqueous phase is reused for the extraction of waste oil.
[0016] As a preferred technical solution, the extraction and separation include: adding an oily extractant and water to the BIPB waste oil phase, stirring and extracting for 20-60 min, separating to obtain an upper oil layer and a lower water layer, the upper oil layer is evaporated to obtain the crude BIPB and the oily extractant, the oily extractant is recycled, and the lower water layer enters the wastewater tank for treatment.
[0017] As a preferred technical solution, the oily extractant is selected from at least one of No. 6 oil, cyclohexane, dichloromethane, ether or carbon tetrachloride, and preferably No. 6 oil.
[0018] As a preferred technical solution, the mass ratio of the BIPB waste oil phase to the oily extractant is 3:(1-2).
[0019] As a preferred technical solution, the mass ratio of the BIPB waste oil phase to water is (3 - 6):1.
[0020] As a preferred technical solution, the conditions for the evaporation treatment are: vacuum degree 0.05 - 0.1 MPa, 60 - 70 °C.
[0021] As a preferred technical solution, the refining method is recrystallization, and the recrystallization includes: after mixing the BIPB crude product with ethanol, controlling the temperature at 40 - 60 °C, and obtaining the BIPB pure product by recrystallization.
[0022] Preferably, the mass ratio of the BIPB crude product to ethanol is 1:(1 - 3).
[0023] The present invention mainly optimizes the design of the recovery and utilization method of BIPB and TBHP in the waste oil generated in the BIPB solvent-free production process. In the exploration of the present invention, it is found that by designing to first add water to the waste oil to extract TBHP to obtain the TBHP wastewater phase and the BIPB waste oil phase, the preliminary separation of BIPB and TBHP is realized, and then the BIPB and TBHP in the TBHP wastewater phase and the BIPB waste oil phase are respectively extracted, separated, and refined to obtain the TBHP pure product and the BIPB pure product. The method is simple and efficient, greatly reducing the treatment cost while realizing the recovery of TBHP and BIPB. Specifically, by controlling the mass ratio of the waste oil to water at 1:(3 - 6), the TBHP in the waste oil is effectively extracted, avoiding the problem that the obtained BIPB waste oil phase is too viscous after extraction, which increases the difficulty of subsequent extraction and separation and cannot obtain a higher purity of BIPB. Further, by subjecting the TBHP wastewater phase to salting-out treatment with an inorganic salt to obtain the TBHP crude product, the TBHP crude product can obtain a TBHP pure product with a purity > 90 wt% through simple filtration. In particular, salting-out treatment is carried out with anhydrous sodium sulfate, and by controlling the addition amount of the inorganic salt at 20 - 40% of the mass of the TBHP wastewater phase, the purity of the subsequent TBHP pure product is ensured.
[0024] Further, by using an oily extractant and water to achieve the extraction and stratification of BIPB, and by controlling the amounts of the oily extractant and water to ensure the extraction and stratification effects, and in combination with the control of the recrystallization temperature, the problem of thermal instability caused by the accelerated self-decomposition is avoided, and a BIPB pure product with a purity > 90 wt% is obtained.
[0025] In addition, the waste brine obtained after salting-out treatment in the method of the present invention can obtain inorganic salts through cooling crystallization. The inorganic salts can be used for salting-out of the next batch of TBHP wastewater phase to achieve recycling; if the salt content in the water phase after crystallization is ≤2 wt%, it can be recycled for extracting the next batch of waste oil; the oily extractant can be recycled after evaporation treatment; the main three wastes in the whole treatment method include the lower layer entering the wastewater tank + the filtered impurities and the ethanol containing organic impurities obtained by recrystallization. The organic components in the lower layer entering the wastewater tank + the filtered impurities are relatively few, and the treatment difficulty is much lower than that of conventional BIPB wastewater, and the ethanol containing organic impurities can obtain relatively pure ethanol through low-temperature recovery, and the remaining impurities can be concentrated for treatment, which reduces the treatment difficulty, reduces the treatment cost, and has a high recycling rate.
[0026] Beneficial effects
[0027] 1. The present invention provides a method for recovering and treating waste oil from the BIPB solvent-free process. The method is simple to operate, not only can it be converted into easily treatable wastewater, but also useful components such as BIPB and TBHP in the waste oil can be recovered to obtain a BIPB product with a relatively high content, which is easy to realize large-scale popularization and application.
[0028] 2. By controlling the mass ratio of waste oil to water to be 1:(3 - 6), the present invention effectively extracts TBHP in the waste oil, avoiding the subsequent increase in the difficulty of extraction and separation due to the excessive viscosity of the BIPB waste oil phase obtained after extraction, and being unable to obtain a BIPB with a relatively high purity.
[0029] 3. By subjecting the TBHP wastewater phase to salting-out treatment with inorganic salts to obtain a crude TBHP product, the crude TBHP product can obtain a TBHP pure product with a purity > 90 wt% through simple filtration. In particular, salting-out treatment with anhydrous sodium sulfate is used, and by controlling the addition amount of the inorganic salt to be 20 - 40% of the mass of the TBHP wastewater phase, the purity of the subsequent TBHP pure product is ensured.
[0030] 4. By using an oily extractant and water to achieve the extraction and stratification of BIPB, controlling the usage amounts of the oily extractant and water to ensure the extraction and stratification effects, and controlling the recrystallization temperature, the problem of thermal instability caused by the accelerated self-decomposition is avoided, and a BIPB pure product with a purity > 90 wt% is obtained.
[0031] 5. The method for recovering and treating waste oil from the BIPB solvent-free process provided by the present invention can extract and remove most of the organic substances in the waste oil, and convert the difficult-to-treat and difficult-to-degrade waste oil into relatively easily treatable wastewater, providing a new idea for the treatment of other chemical waste oils or wastewaters containing a large amount of organic peroxides such as TBHP. Description of the drawings
[0032] Figure 1 Gas chromatogram detection result diagram of pure TBHP obtained in Example 1.
[0033] Figure 2 Liquid chromatogram detection result diagram of pure BIPB obtained in Example 1.
[0034] Figure 3 Gas chromatogram detection result diagram of pure TBHP obtained in Example 2.
[0035] Figure 4 Liquid chromatogram detection result diagram of pure BIPB obtained in Example 2.
[0036] Figure 5 Gas chromatogram detection result diagram of pure TBHP obtained in Example 3.
[0037] Figure 6 Liquid chromatogram detection result diagram of pure BIPB obtained in Example 3. Detailed implementation manners
[0038] Example 1
[0039] Example 1 of the present invention provides a method for recycling and treating waste oil in the BIPB solvent-free process, including the following steps: 100 parts by weight of waste oil are extracted with 400 parts by weight of an extractant and then left to stand for stratification to obtain 423.23 parts by weight of TBHP wastewater phase and 76.77 parts by weight of BIPB waste oil phase; 127.27 parts by weight of inorganic salt are added to the TBHP wastewater phase for salting-out treatment to obtain 48.85 parts by weight of crude TBHP and 501.65 parts by weight of waste brine; the waste brine is recycled; the crude TBHP is purified to obtain 41.97 parts by weight of pure TBHP; the BIPB waste oil phase is subjected to extraction and separation to obtain 46.66 parts by weight of crude BIPB; the crude BIPB is refined to obtain 21.25 parts by weight of pure BIPB.
[0040] The waste oil is from the BIPB solvent-free production process, and its components include BIPB, TBHP and impurities.
[0041] The extractant is water.
[0042] The temperature of the extraction is 25°C and the time is 30 min.
[0043] The inorganic salt is anhydrous sodium sulfate.
[0044] The temperature of the salting-out treatment is 25°C and the time is 30 min.
[0045] The purification method is filtration, and 6.88 parts by weight of impurities after filtration enter the wastewater tank for treatment.
[0046] The recycling of the waste brine includes: obtaining inorganic salts and an aqueous phase by cooling and crystallization of the waste brine, and the inorganic salts are reused for salting-out treatment, and the aqueous phase is reused for waste oil extraction.
[0047] The extraction and separation includes: adding 51.18 parts by weight of an oily extractant and 25.59 parts by weight of water to the BIPB waste oil phase, stirring and extracting for 30 min, separating the liquid to obtain an upper oil layer and a lower water layer, the upper oil layer is subjected to evaporation treatment to obtain BIPB crude product and the oily extractant, and the oily extractant is recycled, and the lower water layer enters the waste water tank for treatment.
[0048] The oily extractant is No. 6 oil.
[0049] The conditions of the evaporation treatment are: vacuum degree 0.08 MPa, 65 °C.
[0050] The refining method is recrystallization, and the recrystallization includes: mixing the BIPB crude product with 23.33 parts by weight of ethanol, controlling the temperature at 50 °C, and obtaining BIPB pure product by primary recrystallization.
[0051] Example 2
[0052] Example 2 of the present invention provides a method for recycling and treating waste oil from a BIPB solvent-free process, including the following steps: 100 parts by weight of waste oil is extracted with 200 parts by weight of an extractant and then left to stand and separate to obtain 213.69 parts by weight of TBHP waste water phase and 86.31 parts by weight of BIPB waste oil phase; 21.37 parts by weight of inorganic salts are added to the TBHP waste water phase for salting-out treatment to obtain 11.05 parts by weight of TBHP crude product and 224.01 parts by weight of waste brine; the waste brine is recycled; the TBHP crude product is purified to obtain 8.66 parts by weight of TBHP pure product; the BIPB waste oil phase is subjected to extraction and separation to obtain 31.68 parts by weight of BIPB crude product; the BIPB crude product is refined to obtain 18.37 parts by weight of BIPB pure product.
[0053] The waste oil is from a BIPB solvent-free production process, and the components include BIPB, TBHP and impurities.
[0054] The extractant is water.
[0055] The temperature of the extraction is 25 °C and the time is 30 min.
[0056] The inorganic salt is anhydrous sodium sulfate.
[0057] The temperature of the salting-out treatment is 25 °C and the time is 30 min.
[0058] The purification method is filtration, and 2.39 parts by weight of impurities after filtration enter the waste water tank for treatment.
[0059] The recycling of the waste brine includes: obtaining inorganic salts and an aqueous phase by cooling and crystallization of the waste brine, and the inorganic salts are reused for salting-out treatment, while the aqueous phase is reused for waste oil extraction.
[0060] The extraction and separation includes: adding 86.31 parts by weight of an oily extractant and 86.31 parts by weight of water to the BIPB waste oil phase, stirring and extracting for 30 min, separating the liquid to obtain an upper oil layer and a lower water layer. After evaporation treatment of the upper oil layer, BIPB crude product and the oily extractant are obtained, and the oily extractant is recycled, while the lower water layer enters the waste water tank for treatment.
[0061] The oily extractant is No. 6 oil.
[0062] The conditions for the evaporation treatment are: vacuum degree 0.08 MPa, 65 °C.
[0063] The refining method is recrystallization, and the recrystallization includes: mixing the BIPB crude product with 31.68 parts by weight of ethanol, controlling the temperature at 50 °C, and obtaining BIPB pure product by primary recrystallization.
[0064] Example 3
[0065] Example 3 of the present invention provides a method for recycling and treating waste oil from the BIPB solvent-free process, including the following steps: 100 parts by weight of waste oil is extracted with 150 parts by weight of an extractant and then allowed to stand and separate to obtain 158.45 parts by weight of TBHP waste water phase and 91.55 parts by weight of BIPB waste oil phase; 23.77 parts by weight of inorganic salts are added to the TBHP waste water phase for salting-out treatment to obtain 9.64 parts by weight of TBHP crude product and 172.58 parts by weight of waste brine; the waste brine is recycled; the TBHP crude product is purified to obtain 6.96 parts by weight of TBHP pure product; the BIPB waste oil phase is subjected to extraction and separation to obtain 40.05 parts by weight of BIPB crude product; the BIPB crude product is refined to obtain 36.05 parts by weight of BIPB pure product.
[0066] The waste oil is from the BIPB solvent-free production process, and its components include BIPB, TBHP and impurities.
[0067] The extractant is water.
[0068] The temperature of the extraction is 25 °C and the time is 30 min.
[0069] The inorganic salt is anhydrous sodium sulfate.
[0070] The temperature of the salting-out treatment is 25 °C and the time is 30 min.
[0071] The purification method is filtration, and 2.68 parts by weight of impurities after filtration enter the waste water tank for treatment.
[0072] The recycling of the waste brine includes: obtaining inorganic salts and an aqueous phase by cooling and crystallization of the waste brine, and the inorganic salts are reused for salting-out treatment, and the aqueous phase is reused for waste oil extraction.
[0073] The extraction and separation includes: adding 137.33 parts by weight of an oily extractant and 137.33 parts by weight of water to the BIPB waste oil phase, stirring and extracting for 30 min, separating the liquid to obtain an upper oil layer and a lower water layer, the upper oil layer is subjected to evaporation treatment to obtain BIPB crude product and the oily extractant, and the oily extractant is recycled, and the lower water layer enters the waste water tank for treatment.
[0074] The oily extractant is ethyl acetate.
[0075] The conditions for the evaporation treatment are: vacuum degree 0.08 MPa, 65 °C.
[0076] The refining method is recrystallization, and the recrystallization includes: mixing the BIPB crude product with 36.05 parts by weight of ethanol, controlling the temperature at 50 °C, and performing primary recrystallization to obtain BIPB pure product.
[0077] Performance test
[0078] 1. The content of TBHP in the TBHP pure product provided in Examples 1-3 was determined by gas chromatography, and the test results are shown in Table 1. Figure 1 、 Figure 3 、 Figure 5 。
[0079] 2. The content of BIPB in the BIPB pure product provided in Examples 1-3 was determined by liquid chromatography, and the test results are shown in Table 1. Figure 2 、 Figure 4 、 Figure 6 。
[0080] Table 1
[0081] Example TBHP content, wt% BIPB content, wt% Example 1 95.98 94.74 Example 2 57.11 80.18 Example 3 62.59 94.25
Claims
1. BIPB solvent-free process waste oil recovery and treatment method, characterized in that: At least the following steps are included: The waste oil is extracted with an extractant and then allowed to stand for stratification to obtain a TBHP wastewater phase and a BIPB waste oil phase; Inorganic salts are added to the TBHP wastewater phase for salting out to obtain TBHP crude product and waste brine; the waste brine is recycled; The crude TBHP product is purified to obtain the pure TBHP product; the BIPB waste oil phase is extracted and separated to obtain the crude BIPB product; the crude BIPB product is refined to obtain the pure BIPB product.
2. The BIPB solvent-free process waste oil recovery and treatment method according to claim 1 is characterized in that: The extractant is selected from at least one of water, methanol, ethanol or acetonitrile.
3. The BIPB solvent-free process waste oil recovery and treatment method according to claim 1 is characterized in that: The mass ratio of the waste oil to the extractant is 1:(3-10).
4. The BIPB solvent-free process waste oil recovery and treatment method according to claim 1 is characterized in that: The inorganic salt is selected from at least one of anhydrous sodium sulfate, sodium chloride, magnesium sulfate or sodium phosphate.
5. The BIPB solvent-free process waste oil recovery and treatment method according to claim 1 is characterized in that: The added amount of the inorganic salt is 20-50% of the mass of the TBHP wastewater phase.
6. The BIPB solvent-free process waste oil recovery and treatment method according to claim 1 is characterized in that: The extraction separation comprises: adding an oily extractant and water to the BIPB waste oil phase, stirring and extracting for 20-60 minutes, separating the liquids to obtain an upper oil layer and a lower water layer, evaporating the upper oil layer to obtain a BIPB crude product and an oily extractant, recycling the oily extractant, and sending the lower water layer into a wastewater pool for treatment.
7. The BIPB solvent-free process waste oil recovery and treatment method according to claim 6 is characterized in that: The oily extractant is selected from at least one of 6# oil, cyclohexane, dichloromethane, ether or carbon tetrachloride.
8. The BIPB solvent-free process waste oil recovery and treatment method according to claim 6 is characterized in that: The mass ratio of the BIPB waste oil phase to the oily extractant is 3:(1-2).
9. The BIPB solvent-free process waste oil recovery and treatment method according to claim 6, characterized in that: The mass ratio of the BIPB waste oil phase to water is (3-6):
1.
10. The BIPB solvent-free process waste oil recovery and treatment method according to claim 1 is characterized in that: The refining method is recrystallization, which includes: mixing the crude BIPB with ethanol, controlling the temperature to 40-60° C., and recrystallizing to obtain pure BIPB.
Citation Information
Patent Citations
Hydrogenation method of high-purity dimer acid
CN118791378A