阅读说明：本技术 一种废弃全氟聚醚润滑油的催化裂解方法 (Catalytic cracking method of waste perfluoropolyether lubricating oil ) 是由 张永奎 杜鑫航 李盼禹 罗佳 于 2021-08-19 设计创作，主要内容包括：本发明提供一种废弃全氟聚醚润滑油的催化裂解方法,以MnO-(2)为催化剂,Na-(2)CO-(3)为含氟气体固定剂,使得全氟聚醚润滑油中的有机氟转移至更易处理的水相无机氟离子本发明具有以下优点：本发明工业用MnO-(2)与Na-(2)CO-(3)价格低廉,原料广泛,处理全氟聚醚润滑油的工艺过程简单,易于工业化应用。)MnO-(2)为裂解全氟聚醚润滑油有效的催化剂,脱氟率可达到99%,且在恰当条件下MnO-(2)可重复循环利用。运用Na-(2)CO-(3)固定含氟气体,避免释放含氟气体对人体和环境造成危害。(The invention provides a catalytic cracking method of waste perfluoropolyether lubricating oil, which uses MnO 2 As catalyst, Na 2 CO 3 The fluorine-containing gas fixing agent enables organic fluorine in the perfluoropolyether lubricating oil to be transferred to aqueous phase inorganic fluoride ions which are easier to treat, and the method has the following advantages: MnO for industry of the invention 2 With Na 2 CO 3 Low cost, wide raw material, simple process for treating perfluoropolyether lubricating oil and easy industrial application。）MnO 2 Effective catalyst for cracking perfluoropolyether lubricating oil, defluorination rate can reach 99%, and MnO is added under proper conditions 2 Can be repeatedly recycled. By applying Na 2 CO 3 The fluorine-containing gas is fixed, and the harm to human bodies and the environment caused by the release of the fluorine-containing gas is avoided.)

1. The catalytic cracking method of the waste perfluoropolyether lubricating oil is characterized in that MnO is used₂As catalyst, Na₂CO₃The fluorine-containing gas fixing agent enables organic fluorine in the perfluoropolyether lubricating oil to be transferred to aqueous phase inorganic fluoride ions which are easier to process.

2. The method of claim 1, wherein MnO is added to the waste perfluoropolyether lubricating oil₂Perfluoropolyether lubricating oils and Na₂CO₃Mixing and heating to crack the lubricating oil completely.

3. The method of claim 1, wherein the perfluoropolyether lubricating oil is MnO₂The mass ratio is 1:2-1: 60; na (Na)₂CO₃Comprising perfluoropolyether lubricating oils and MnO₂20-100% of the mass sum.

4. The catalytic cracking method of waste perfluoropolyether lubricating oil as claimed in claim 1, wherein the heating treatment is carried out at a temperature of 300 ℃ and 1000 ℃ and at a temperature rise rate of 0-20 ℃/min for 1-12 h.

Technical Field

The invention belongs to the field of waste treatment, particularly relates to a catalytic cracking method of waste perfluoropolyether lubricating oil, and particularly relates to a method for utilizing MnO₂，Na₂CO₃A process for catalytically cracking waste perfluoropolyether lubricating oils at high temperatures.

Background

Perfluoropolyether lubricating oil (PFPE) is a perfluoropolymer compound and is widely applied to aerospace and various harsh environments. The molecule only consists of three elements of C, F and O, and fluorine atoms have strong electronegativity (the C-F bond energy is as high as 418.4-502.08 k J/mo1), and carbon chains are shielded by the fluorine atoms. Accordingly, perfluoropolyethers have many excellent properties compared to hydrocarbon polyethers, such as chemical inertness, thermo-oxidative stability, compatibility, flame resistance, radiation resistance, and the like.

Perfluoropolyether lubricating oils deteriorate during continuous use due to various reasons such as excessive ambient temperatures, and become "waste lubricating oils". The waste perfluoropolyether lubricating oil is accumulated to occupy a large space and can be subjected to slow oxidative cracking in the air to release various fluorine-containing small-molecule gases (such as F) harmful to human bodies and the environment₂，CF₄，COF₂Etc.), because of the extremely high chemical stability of perfluoropolyether lubricating oil, no method for treating waste perfluoropolyether lubricating oil is reported at present, and the difficulty lies in effective cracking and fixation of fluorine-containing gas after cracking, so that the method for efficiently and environmentally treating waste perfluoropolyether lubricating oil is sought, which is not slow.

Disclosure of Invention

The invention aims to provide a catalytic cracking method of waste perfluoropolyether lubricating oil by using MnO₂，Na₂CO₃And (3) carrying out high-temperature catalytic cracking on the waste perfluoropolyether lubricating oil.

The invention is realized by the following technical scheme.

Catalytic cracking method of waste perfluoropolyether lubricating oil, using MnO₂As catalyst, Na₂CO₃As a fluorine-containing gas fixing agent to make the transfer of organic fluorine in perfluoropolyether lubricating oils easier to handleInorganic fluoride ion in water phase.

The method specifically comprises the following steps:

(1) MnO of₂Perfluoropolyether lubricating oils and Na₂CO₃Mixing at a certain ratio. Wherein the perfluoropolyether lubricating oil: MnO₂ The mass of (1: 2) - (1: 60) is Na₂CO₃Comprising perfluoropolyether lubricating oils and MnO₂20-100% of the mass sum.

(2) And transferring the mixed substances into a pyrolysis device for heating reaction. Wherein the reaction temperature is 300 ℃ and 1000 ℃, the heating rate is 0-20 ℃/min, and the reaction time is 1-12 h.

The invention has the following advantages:

(1) MnO for industry₂ With Na₂CO₃Low price, wide raw materials, simple process for treating the perfluoropolyether lubricating oil and easy industrial application.

（2）MnO₂Effective catalyst for cracking perfluoropolyether lubricating oil, defluorination rate can reach 99%, and MnO is added under proper conditions₂Can be repeatedly recycled.

(3) By applying Na₂CO₃The fluorine-containing gas is fixed, and the harm to human bodies and the environment caused by the release of the fluorine-containing gas is avoided.

Drawings

FIG. 1 is a graph showing the comparison of X-ray diffraction patterns before and after the reaction of the catalyst of the present invention at 600 ℃.

FIG. 2 is a graph showing the comparison of X-ray diffraction patterns before and after the reaction of the catalyst of the present invention at 400 ℃.

Detailed Description

For a better understanding of the invention, it will be further explained below with reference to the embodiment examples and the accompanying drawings. It should be noted that the embodiments are only used for further explaining the invention, and the scope of the invention to be claimed is not limited to the scope shown in the embodiments.

Examples 1

60 mg of perfluoropolyether lubricating oil and 2.5g of MnO were weighed₂Mixing, transferring into 50ml crucible, and spreading 2.5g Na on the mixture₂CO₃The mixture is transferred into a muffle furnace, the reaction temperature is 600 ℃, the heating rate is 5 ℃/min, and the reaction time is 3 h. After the reaction is finished, taking out the crucible after the temperature of the muffle furnace is reduced to room temperature, transferring the reacted substances in the crucible to a plastic beaker, adding distilled water until the total volume is 200ml, and dropwise adding concentrated sulfuric acid under the stirring state until the pH is = 1. After stirring for 3 hours, the mixture was filtered, and the defluorination rate was measured.

EXAMPLES example 2

60 mg of perfluoropolyether lubricating oil and 2.4g of MnO were weighed₂Mixing, transferring into 50ml crucible, and spreading 2g Na on the mixture₂CO₃The mixture is transferred into a muffle furnace, the reaction temperature is 400 ℃, the heating rate is 5 ℃/min, and the reaction time is 3 h. After the reaction is finished, taking out the crucible after the temperature of the muffle furnace is reduced to room temperature, transferring the reacted substances in the crucible to a plastic beaker, adding distilled water until the total volume is 200ml, dropwise adding concentrated sulfuric acid under the stirring state until the pH is =1, stirring for 3h, filtering, and measuring the defluorination rate.

EXAMPLE 3

160 mg of perfluoropolyether lubricating oil and 2.5g of MnO were weighed₂Mixing, transferring into 50ml crucible, and covering the above mixed material with 2g Na₂CO₃The mixture is transferred into a muffle furnace, the reaction temperature is 800 ℃, the heating rate is 10 ℃/min, and the reaction time is 1 h. After the reaction is finished, taking out the crucible after the temperature of the muffle furnace is reduced to room temperature, transferring the reacted substances in the crucible to a plastic beaker, adding distilled water until the total volume is 200ml, dropwise adding concentrated sulfuric acid under the stirring state until the pH is =1, stirring for 3h, filtering, and measuring the defluorination rate.

As shown in FIG. 1, the catalyst is MnO before the reaction₂MnO after reaction at 600 ℃₂High temperature deoxidation to Mn₂O₃。

As shown in FIG. 2, MnO was not reached due to the reaction at 400 ℃₂The deoxidation temperature is high, so that the catalyst is MnO before and after the reaction₂。

In the invention, MnO is used₂Is a high-efficiency and environment-friendly catalyst, Na₂CO₃Is an effective fluorine-containing gas fixing agent, and can be used under optimum reaction conditionsThe organic fluorine in the fluoropolyether lubricating oil is completely transferred to the inorganic fluorine ions in the water phase which is easier to treat, and the ratio of the inorganic fluorine ions transferred to the water phase to the fluorine in the perfluor is the defluorination rate. The defluorination rate of the method can approach to 99 percent, so the method can be used as a good treatment method for the waste perfluoropolyether lubricating oil, and has good application prospect.