Method for recovering methyl hexynediol from residual waste liquid of methyl butynol heavy component removal kettle
Methylhexynediol is recovered through steps of vacuum filtration, distillation, recrystallization, rinsing and drying, which solves the problems of resource waste and environmental pollution in the residue of methylbutynediol desulfurization reactor, achieves efficient and environmentally friendly resource recovery, and has the potential for industrial application.
Patent Information
- Application Number
- CN202511150227.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-18
- Publication Date
- 2025-12-02
AI Technical Summary
In the existing technology, the method for recovering methylhexynediol from the waste liquid generated in the de-heavy residue of the methylbutynediol production process is not mature, which leads to resource waste and environmental pollution, and the existing treatment methods do not conform to the concept of green and sustainable development.
Methylhexynyl diol is recovered by means of vacuum filtration, vacuum distillation, recrystallization, vacuum filtration, rinsing and drying. Specifically, it includes vacuum filtration to remove impurities, vacuum distillation to separate the mixture, recrystallization for purification, rinsing and drying of the solid, with toluene preferably used as the rinsing solvent.
It achieves high yield (over 68%) and high purity (over 98%) of methylhexynediol, reduces the cost of waste treatment, and has a simple and easy-to-operate process with industrial application value.
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Figure CN121044964A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of waste liquid recycling technology, and in particular relates to a method for recovering methylhexynediol from the residual liquid of methylbutynol decontamination reactor. Background Technology
[0002] Methylbutynol, also known as 2-methyl-3-butyn-2-ol, has the molecular formula C5H8O and a molecular weight of 84.12. It is an important alkynol organic compound with dual functional groups of alkyne bond and hydroxyl group. Currently, the most common industrial synthesis method for methylbutynol involves a nucleophilic addition reaction between a terminal alkyne (acetylene) and a ketone (acetone) under strong base catalysis to yield products such as methylbutynol, methylhexynediol, and isopropylidene acetone alcohol. However, the industrial production of methylbutynol generates a waste liquid from the de-heavy residue reactor containing methylhexynediol.
[0003] Methylhexyndiol, also known as 2,5-dimethyl-3-hexyn-2,5-diol, has the molecular formula C8H10. 14 O2, with a molecular weight of 142.2, is a high-value-added chemical intermediate that can be used in the synthesis of pharmaceuticals, pesticides, and fine chemicals. For example, methylhexynylene glycol can be used in industrial production not only as a synthetic intermediate for herbicides, lubricants, adhesives, and defoamers, but also as a raw material for the synthesis of surfactants, insecticides, and fragrances.
[0004] Currently, existing production workshops typically treat the waste liquid from the deconsolidation reactor containing methylhexynediol generated during the production of methylbutynol by incineration. This method not only wastes resources and causes environmental pollution but also increases the cost of waste treatment, which is inconsistent with the concept of green and sustainable development. Furthermore, current technologies lack a process strategy for recovering methylhexynediol from the waste liquid from the deconsolidation reactor of methylbutynol.
[0005] Therefore, developing an efficient and environmentally friendly method for recovering methylhexynediol from the waste liquid of methylbutynol desulfurization reactor has significant economic and social benefits. Summary of the Invention
[0006] In order to overcome the shortcomings of the prior art, one of the objectives of this invention is to provide a method for recovering methylhexynediol from the waste liquid of methylbutynol decontamination reactor, which can solve the problem of recovering methylhexynediol from the waste liquid of methylbutynol decontamination reactor.
[0007] To achieve the above objectives, the present invention employs the following technical solution:
[0008] A method for recovering methylhexynediol from the residue of methylbutynol removal reactor includes the following steps:
[0009] The residual liquid from the de-heavy alcohol desulfurization reactor containing methylhexynylenediol is filtered under reduced pressure, and then the filtrate is subjected to reduced pressure distillation. The unseparated mixture after reduced pressure distillation is recrystallized and then filtered under reduced pressure again. The solid obtained from the reduced pressure filtration is washed and dried to obtain the methylhexynylenediol product. The pressure of the reduced pressure distillation is -50k to -98kPa, and the temperature is 40 to 62℃.
[0010] Preferably, the pressure of the vacuum filtration is -0.06 to -0.1 MPa. More preferably, it is -0.1 MPa. The first vacuum filtration removes insoluble impurities such as black tar from the residual liquid. The second vacuum filtration effectively separates the recrystallized product from the filtrate.
[0011] Preferably, the pressure of the vacuum distillation process is -92kPa to -97kPa, and the temperature is 49.5 to 61.1℃. During this step, the vacuum distillation is terminated when the material in the distillation system reaches its highest distillation temperature and no obvious fractions remain. By controlling the vacuum distillation process, the yield and purity of the product can be further improved.
[0012] Preferably, the recrystallization temperature is -16~30℃ and the time is 1~5h.
[0013] Preferably, the solvent used for rinsing is one or more of toluene, benzene, cyclohexane, and isopropyl acetate.
[0014] More preferably, the solvent used for rinsing is toluene. Screening experiments on rinsing solvents revealed that using toluene as the rinsing solvent yields the best rinsing effect, resulting in the highest purity of the methylhexynediol product.
[0015] Preferably, the rinsing is performed 2 to 5 times. More preferably, the rinsing is performed 3 times.
[0016] Preferably, the total mass of the solvent used for rinsing is 2 to 4 times the mass of the solids, more preferably 3 times.
[0017] Preferably, the drying is vacuum drying or atmospheric pressure drying.
[0018] More preferably, the drying temperature is 50~80℃, and the drying time is 1~5h. More preferably, the vacuum degree of the vacuum drying is 0~-95kPa.
[0019] The beneficial effects of the above-mentioned technical solution of the present invention are as follows:
[0020] The method for recovering methylhexynediol from the residue of methylbutynol desulfurization reactor provided by this invention, through a series of steps including vacuum filtration, vacuum distillation, recrystallization, vacuum filtration, rinsing, and drying, can effectively recover methylhexynediol from the residue of methylbutynol desulfurization reactor, with a product yield of over 68% and a product purity of over 98%. Therefore, it can effectively realize waste utilization and reduce the cost of waste treatment.
[0021] Furthermore, the recycling method provided by this invention has a simple and easy-to-operate process, is easy to industrialize, and has strong industrial application value and economic benefits. It can also provide a simple and efficient process strategy for the recovery of methylhexynediol from the residue of the methylbutynediol desulfurization reactor. Attached Figure Description
[0022] Figure 1 This is a gas chromatogram of the methylhexynediol product recovered in Example 1 of the present invention. Detailed Implementation
[0023] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. It should be noted that, without conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments. Specific conditions not specified in the embodiments are performed according to conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, all materials used are conventional products obtained through commercial channels.
[0024] The present invention provides a method for recovering methylhexynediol from the residue of methylbutynol removal reactor, comprising the following steps:
[0025] The residual liquid from the de-heavy alcohol desulfurization reactor containing methylhexynylenediol is filtered under reduced pressure, and then the filtrate is subjected to reduced pressure distillation. The unseparated mixture after reduced pressure distillation is recrystallized and then filtered under reduced pressure again. The solid obtained from the reduced pressure filtration is washed and dried to obtain the methylhexynylenediol product. The pressure of the reduced pressure distillation is -50k to -98kPa, and the temperature is 40 to 62℃.
[0026] In a preferred embodiment, the pressure of the pressure-reducing filter is -0.06 to -0.1 MPa. In the following embodiments, the pressure of the pressure-reducing filter is -0.1 MPa.
[0027] As a preferred embodiment, the pressure of vacuum distillation is -92k~-97kPa and the temperature is 49.5~61.1℃.
[0028] As a preferred embodiment, the recrystallization temperature is -16~30°C and the time is 1~5h.
[0029] As a preferred embodiment, the solvent used for rinsing is one or more of toluene, benzene, cyclohexane, and isopropyl acetate.
[0030] In a preferred embodiment, toluene is used as the solvent for rinsing.
[0031] In a preferred embodiment, the rinsing is performed 2 to 5 times. More preferably, the rinsing is performed 3 times.
[0032] In a preferred embodiment, the total mass of the solvent used for rinsing is 2 to 4 times the mass of the solids, more preferably 3 times.
[0033] As a preferred embodiment, the drying is vacuum drying or atmospheric pressure drying.
[0034] In a preferred embodiment, the drying temperature is 50~80℃, and the drying time is 1~5h. More preferably, the vacuum degree of vacuum drying is 0~-95kPa.
[0035] Example 1
[0036] This embodiment provides a method for recovering methylhexynediol from the residue of methylbutynol removal reactor, comprising the following steps:
[0037] 1777.13 g of the residue from the methylbutynin alcohol de-removal reactor containing 25.67 wt% methylhexynylene diol was taken and filtered under reduced pressure to remove insoluble black impurities. The filtrate was placed in a 3000 mL flask and heated under reduced pressure at -96 kPa to -97 kPa. Distillation was stopped when the temperature reached 49.5 °C, yielding 444.53 g of fraction. The unseparated mixture after reduced pressure distillation was placed at -16 °C for 2 h for recrystallization. After recrystallization, it was filtered under reduced pressure. Toluene was then added to the filtered solid for rinsing three times, with the total amount of toluene added being three times the mass of the filtered solid. After rinsing, the filter cake was dried in a drying oven at normal pressure at 60 °C for 2 h. The dried product was a pale yellow methylhexynylene diol with a mass of 350.72 g.
[0038] The purity of the methylhexynediol product recovered in Example 1 was tested by gas chromatography, and the resulting gas chromatogram is shown below. Figure 1 As shown in Table 1, the gas chromatography analysis results are as follows.
[0039] Table 1. Gas chromatographic analysis results of the methylhexynediol product prepared in Example 1
[0040]
[0041]
[0042] Depend on Figure 1 As shown in Table 1, the purity of the methylhexynediol product prepared in Example 1 is 99.18%. Further calculation using the yield formula (yield (%) = 100% × (product mass × purity) / (total mass of residual liquid × content)) shows that the total yield of methylhexynediol is 76.24%.
[0043] Example 2
[0044] This embodiment provides a method for recovering methylhexynediol from the residue of methylbutynol removal reactor, comprising the following steps:
[0045] 531.86 g of the residue from the methylbutynin alcohol de-stabilization reactor containing 26.16 wt% methylhexynylene diol was taken and filtered under reduced pressure to remove insoluble black impurities. The filtrate was placed in a 1000 mL flask and heated under reduced pressure at -92 kPa to -96 kPa. Distillation was stopped when the temperature reached 60 °C, yielding 42.35 g of fraction. The unseparated mixture after reduced pressure distillation was placed in primary water at 28 °C for 2 h for recrystallization. The recrystallized solid was hard and soaked in toluene overnight. Then, it was filtered under reduced pressure. Subsequently, toluene was added to the filtered solid for rinsing, and the rinsing was repeated 4 times. The total amount of toluene added was 4 times the mass of the filtered solid. After rinsing, the filter cake was placed in a drying oven for drying at normal pressure at 70 °C for 3 h. After drying, a pale yellow methylhexynylene diol product was obtained, with a product mass of 97.04 g.
[0046] The purity of the methylhexynediol product recovered in Example 2 was tested by gas chromatography, and the purity of the methylhexynediol product obtained by gas chromatography was 98.78%. Further calculation using the yield formula (yield (%) = 100% × (product mass × purity) / (total mass of residual liquid × content)) showed that the total yield of methylhexynediol was 68.90%.
[0047] Example 3
[0048] This embodiment provides a method for recovering methylhexynediol from the residue of methylbutynol removal reactor, comprising the following steps:
[0049] 1328.63 g of the residue from the methylbutynin alcohol de-removal reactor containing 30.35 wt% methylhexynylene diol was first filtered under reduced pressure to remove insoluble black impurities. The filtrate was placed in a 2000 mL flask and heated under reduced pressure at -92 kPa to -94 kPa. Distillation was stopped when the temperature reached 61.1 °C, yielding 299.95 g of fraction. The unseparated mixture after reduced pressure distillation was placed in primary water at 26 °C and allowed to stand for 2 h for recrystallization. After recrystallization, the mixture was filtered under reduced pressure. Toluene was then added to the filtered solid for rinsing three times, with the total amount of toluene added being three times the mass of the filtered solid. After rinsing, the filter cake was dried in a drying oven at normal pressure at 70 °C for 2 h. The dried product was a pale yellow methylhexynylene diol with a mass of 290.30 g.
[0050] The purity of the methylhexynediol product recovered in Example 3 was tested by gas chromatography, and the purity of the methylhexynediol product obtained by gas chromatography was 99.29%. Further calculation using the yield formula (yield (%) = 100% × (product mass × purity) / (total mass of residual liquid × content)) showed that the total yield of methylhexynediol was 71.48%.
[0051] Comparative Example 1
[0052] This comparative example provides a method for recovering methylhexynediol from the residue of the methylbutynol desulfurization reactor. The recovery process is based on the same as in Example 1, with the only difference being the temperature of the vacuum distillation process. In this comparative example, vacuum distillation is carried out under heating at -96 kPa to -97 kPa, and the distillation is stopped when the temperature reaches 65°C. Other processes and parameters are the same as in Example 1.
[0053] The purity of the methylhexynediol product recovered from the comparative example was tested by gas chromatography, and the purity of the methylhexynediol product obtained by gas chromatography was 99.25%. Further calculation using the yield formula (yield (%) = 100% × (product mass × purity) / (total mass of residual liquid × content)) showed that the total yield of methylhexynediol was 70.52%.
[0054] Comparative Example 2
[0055] This comparative example provides a method for recovering methylhexynyl diol from the residue of the methylbutynol desulfurization reactor. The recovery process is based on the same as in Example 1, with the only difference being the temperature of the vacuum distillation process. In this comparative example, vacuum distillation is carried out under heating at -96 kPa to -97 kPa, and the distillation is stopped when the temperature reaches 30°C. Other processes and parameters are the same as in Example 1.
[0056] The purity of the methylhexynediol product recovered in the comparative example was tested by gas chromatography, and the purity of the methylhexynediol product obtained by gas chromatography was 97.15%. Further calculation using the yield formula (yield (%) = 100% × (product mass × purity) / (total mass of residual liquid × content)) showed that the total yield of methylhexynediol was 77.53%.
[0057] Comparative Example 3
[0058] This comparative example provides a method for recovering methylhexynyl diol from the residue of the methylbutynol desulfurization reactor. The recovery process is based on the same as in Example 1, with the only difference being the rinsing solvent. In this comparative example, benzene is used as the rinsing solvent, and other processes and parameters are the same as in Example 1.
[0059] The purity of the methylhexynediol product recovered from the comparative example was tested by gas chromatography, and the purity of the methylhexynediol product obtained by gas chromatography was 96.55%. Further calculation using the yield formula (yield (%) = 100% × (product mass × purity) / (total mass of residual liquid × content)) showed that the total yield of methylhexynediol was 77.15%.
[0060] Comparative Example 4
[0061] This comparative example provides a method for recovering methylhexynyl diol from the residue of the methylbutynol desulfurization reactor. The recovery process is based on the same as in Example 1, with the only difference being the rinsing solvent. In this comparative example, cyclohexane is used as the rinsing solvent, and other processes and parameters are the same as in Example 1.
[0062] The purity of the methylhexynediol product recovered in the comparative study was tested using gas chromatography, and the purity of the methylhexynediol product obtained by gas chromatography was 96.92%. Further calculation using the yield formula (yield (%) = 100% × (product mass × purity) / (total mass of residual liquid × content)) showed that the total yield of methylhexynediol was 80.23%.
[0063] Based on the above experimental results, the method for recovering methylhexynyl diol from the residue of the methylbutynol removal reactor provided by this invention achieves a product yield of over 68% and a product purity of over 98%, thus achieving a balance between product yield and purity. In contrast, the recovery method provided in the comparative example cannot achieve a balance between product yield and purity, failing to meet quality requirements.
[0064] Therefore, this invention, through a series of steps including vacuum filtration, vacuum distillation, recrystallization, vacuum filtration, rinsing, and drying, can effectively recover methylhexynediol from the residue of methylbutynol desulfurization reactor, with high product yield and purity. It has strong industrial application value and economic benefits, and can also provide a simple and efficient process strategy for the recovery of methylhexynediol from the residue of methylbutynol desulfurization reactor.
[0065] The above embodiments are merely preferred embodiments of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention shall fall within the scope of protection claimed by the present invention.
Claims
1. A method for recovering methylhexynediol from the residue of methylbutynol desulfurization reactor, characterized in that, Includes the following steps: The residual liquid from the de-heavy alcohol desulfurization reactor containing methylhexynylenediol is filtered under reduced pressure, and then the filtrate is subjected to reduced pressure distillation. The unseparated mixture after reduced pressure distillation is recrystallized and then filtered under reduced pressure again. The solid obtained from the reduced pressure filtration is washed and dried to obtain the methylhexynylenediol product. The pressure of the reduced pressure distillation is -50k to -98kPa, and the temperature is 40 to 62℃.
2. The method for recovering methylhexynediol from the residue of the methylbutynol desulfurization reactor according to claim 1, characterized in that, The pressure of the pressure-reducing filter is -0.06 to -0.1 MPa.
3. The method for recovering methylhexynediol from the residue of the methylbutynol desulfurization reactor according to claim 1, characterized in that, The pressure of the vacuum distillation process is -92k to -97kPa, and the temperature is 49.5 to 61.1℃.
4. The method for recovering methylhexynediol from the residue of the methylbutynol desulfurization reactor according to claim 1, characterized in that, The recrystallization temperature is -16~30℃, and the time is 1~5h.
5. The method for recovering methylhexynediol from the residue of the methylbutynol desulfurization reactor according to claim 1, characterized in that, The solvent used for rinsing is one or more of toluene, benzene, cyclohexane, and isopropyl acetate.
6. The method for recovering methylhexynediol from the residue of the methylbutynol desulfurization reactor according to claim 5, characterized in that, The solvent used for rinsing is toluene.
7. The method for recovering methylhexynediol from the residue of the methylbutynol desulfurization reactor according to any one of claims 1 to 5, characterized in that, The rinsing process is repeated 2 to 5 times.
8. The method for recovering methylhexynediol from the residue of the methylbutynol desulfurization reactor according to any one of claims 1 to 5, characterized in that, The total mass of the solvent used for rinsing is 2 to 4 times the mass of the solid.
9. The method for recovering methylhexynediol from the residue of the methylbutynol desulfurization reactor according to any one of claims 1 to 5, characterized in that, The drying process is either vacuum drying or atmospheric pressure drying.
10. The method for recovering methylhexynediol from the residue of the methylbutynol desulfurization reactor according to claim 9, characterized in that, The drying temperature is 50~80℃, and the drying time is 1~5h.