阅读说明：本技术 一种废机油类的低阶煤捕收剂的氧化改良方法 (Oxidation improvement method for waste machine oil low-rank coal collecting agent ) 是由 廖寅飞 杨哲 刘泽晨 安茂燕 曹亦俊 马子龙 于 2021-07-20 设计创作，主要内容包括：本发明公开了一种废机油类的低阶煤捕收剂的氧化改良方法,包括以下步骤：(1)配制pH值为3.5-5.5的过氧化氢水溶液作为废机油的氧化药剂；(2)将步骤(1)配制的过氧化氢水溶液和废机油原料投入反应釜中,控制反应时间在0.5-2h,控制反应温度在20-40℃；(3)反应完成后,将反应釜内的产物进行过滤,去除废渣和化学沉淀物,得到改良后的低阶煤捕收剂。本发明处理后的废机油,成分被改良,粘度下降,废机油中的重金属离子和固体被氧化形成废渣,被过滤除去,一定程度上降低了废机油的污染性。本发明“变废为宝”有效地将废机油转化为高效低阶煤浮选捕收剂,具有效果好、成本低和污染小的优点,实现了资源的循环利用。(The invention discloses an oxidation improvement method of a waste machine oil low-rank coal collecting agent, which comprises the following steps: (1) preparing hydrogen peroxide aqueous solution with the pH value of 3.5-5.5 as an oxidation agent of the waste engine oil; (2) putting the aqueous hydrogen peroxide solution prepared in the step (1) and the waste engine oil raw materials into a reaction kettle, controlling the reaction time to be 0.5-2h and the reaction temperature to be 20-40 ℃; (3) and after the reaction is finished, filtering the product in the reaction kettle, and removing waste residues and chemical precipitates to obtain the improved low-rank coal collecting agent. The waste engine oil treated by the method has the advantages of improved components, reduced viscosity, and reduced pollution of the waste engine oil to a certain extent, because heavy metal ions and solids in the waste engine oil are oxidized to form waste residues which are filtered and removed. The method changes waste oil into waste oil effectively, has the advantages of good effect, low cost and little pollution, and realizes the cyclic utilization of resources.)

1. An oxidation improvement method of a low-rank coal collector of waste machine oil is characterized by comprising the following steps: the method comprises the following steps:

(1) preparing hydrogen peroxide aqueous solution with the pH value of 3.5-5.5 as an oxidation agent of the waste engine oil;

(2) putting the aqueous hydrogen peroxide solution prepared in the step (1) and the waste engine oil raw materials into a reaction kettle, controlling the reaction time to be 0.5-2h and the reaction temperature to be 20-40 ℃;

(3) and after the reaction is finished, filtering the product in the reaction kettle, and removing waste residues and chemical precipitates to obtain the improved low-rank coal collecting agent.

2. The method for improving the oxidation of the waste machine oil type low-rank coal collector according to claim 1, wherein the method comprises the following steps: in the step (1), the mass concentration of the aqueous hydrogen oxide solution is 20-40%; adjusting the pH value of the aqueous solution of hydrogen peroxide by using NaOH and sulfuric acid, and adjusting the pH range of the solution to 3.5-4.5 when the mass concentration of the prepared aqueous solution of hydrogen peroxide is 20-30%; when the mass concentration of the prepared hydrogen peroxide solution is 30-40%, the pH range of the solution is adjusted to 4.5-5.5.

3. The method for improving the oxidation of the waste machine oil type low-rank coal collector according to claim 1, wherein the method comprises the following steps: in the step (2), the used engine oil raw material is used engine oil or used lubricating oil which takes hydrocarbon, alkane, arene and PAO polymers as the main components of base oil; used oil feedstocks are derived from oils that are mechanically rubbed, degraded in lubrication performance by high temperatures.

4. The oxidation upgrading method of the waste machine oil type low-rank coal collector according to claim 1 or 2, characterized in that: in the step (2), the dynamic viscosity of the used oil raw material is lower than 180mP & s.

5. The method for improving the oxidation of the waste machine oil type low-rank coal collector according to claim 1, wherein the method comprises the following steps: in the step (2), the aqueous hydrogen peroxide solution accounts for 5-15% of the mass of the raw material of the waste engine oil.

6. The method for improving the oxidation of the waste machine oil type low-rank coal collector according to claim 1, wherein the method comprises the following steps: for the used engine oil raw material with the acid value of less than 4mg KOH/g or the dynamic viscosity of more than 120 mPas, the mass concentration of the hydrogen peroxide aqueous solution is 30-40 percent, and the reaction time is 1.5-2 h.

7. The method for improving the oxidation of the waste machine oil type low-rank coal collector according to claim 1, wherein the method comprises the following steps: the reaction kettle is a steel-lined tetrafluoroethylene reaction kettle, and the stirring mode in the reaction kettle is spiral ribbon stirring.

8. The method for improving the oxidation of the waste machine oil type low-rank coal collector according to claim 1, wherein the method comprises the following steps: in the step (3), 1-2 filter screens are used during filtering, and the aperture of each filter screen is 100-200 meshes.

Technical Field

The invention belongs to the technical field of mineral flotation, and relates to a method for improving waste engine oil as a coal slime flotation collector.

Background

The low-rank coal is the most main coal type in Chinese coal resources and accounts for about 45 percent of the Chinese coal reserves. The energy structure mainly made of coal is the foothold and the foundation of the development of China at present. The efficient clean utilization of low-rank coal is one of the problems of the current coal utilization. The low-rank coal slurry has high yield and fine granularity, and the separation and enrichment of the low-rank coal by flotation is one of the main means for treating the low-rank coal at present. However, the low-rank coal is low in coalification degree, the number of oxygen-containing functional groups on the surface is large, the types are rich, and a good flotation index is difficult to obtain by using a conventional flotation collector, so that a high-quality low-rank coal product is difficult to obtain.

Used oil is a state-regulated hazardous waste. The used oil is mainly composed of a large amount of aromatic hydrocarbon components and alkane components. The proportion of the oxidation substances such as carboxylic acid, ester, ketone, alcohol and the like is reported to be lower and less than 20 percent. Heavy metal ions, mechanical impurities and solid impurities in the waste engine oil are more. In 2018, the consumption of the lubricating oil in China is about 880 ten thousand tons, and according to the estimation of the elimination rate of the lubricating oil in China of 60 percent, in China, about 490 ten thousand tons of waste lubricating oil are generated every year. The automobile and automobile disassembly industry in China can produce a large amount of waste engine oil every year.

The waste engine oil can be used as a coal slime flotation collector with a good effect. The flotation collector is adsorbed on the surface of coal slime to enhance the hydrophobicity of the surface of coal, so that the coal is easier to separate from gangue in flotation. The selectivity and the collector performance of the collector are two important indexes for measuring the performance of the collector. Coal is heterogeneous organic rock, and the lower the coalification degree, the more alkane side chains and oxygen-containing functional groups are on the surface of the coal. Therefore, the collector is preferably a reasonably composed mixture of various nonpolar hydrocarbon oils. The oxygen-containing functional groups on the surface of the low-rank coal are rich in impurities, so that the effect of using the oxygen-containing organic oil as the collecting agent is better. The waste engine oil contains various oxidized organic matters, alkane and aromatic hydrocarbon, and can enhance the flotation effect of low-rank coal to a certain extent. The waste engine oil is oxidized and improved by a controllable oxidation method, so that the content of various oxygen-containing organic matters can be increased, and the performance of the waste engine oil as a low-rank coal flotation collector is further enhanced; various metal ions and solid impurities in the waste engine oil form precipitated waste residues under the oxidation reaction, and the precipitated waste residues are filtered and separated from the waste engine oil, so that the pollution of the waste engine oil can be reduced.

Disclosure of Invention

The invention aims to provide an oxidation improvement method of a low-rank coal collecting agent of waste engine oil, so as to enhance the effect of the waste engine oil in the application of the low-rank coal collecting agent and enable the application process of the waste engine oil to be cleaner and more environment-friendly.

An oxidation improvement method of a low-rank coal collector of waste engine oil comprises the following steps:

(1) preparing hydrogen peroxide aqueous solution with the pH value of 3.5-5.5 as an oxidation agent of the waste engine oil;

(2) putting the aqueous hydrogen peroxide solution prepared in the step (1) and the waste engine oil raw materials into a reaction kettle, controlling the reaction time to be 0.5-2h and the reaction temperature to be 20-40 ℃;

(3) and after the reaction is finished, filtering the product in the reaction kettle, and removing waste residues and chemical precipitates to obtain the improved low-rank coal collecting agent.

Further, in the step (1), the mass concentration of the aqueous hydrogen oxide solution is 20-40%; adjusting the pH value of the aqueous solution of hydrogen peroxide by using NaOH and sulfuric acid, and adjusting the pH range of the solution to 3.5-4.5 when the mass concentration of the prepared aqueous solution of hydrogen peroxide is 20-30%; when the mass concentration of the prepared hydrogen peroxide solution is 30-40%, the pH range of the solution is adjusted to 4.5-5.5.

Further, in the step (2), the used engine oil raw material is used engine oil or used lubricating oil which takes hydrocarbon, alkane, aromatic hydrocarbon and PAO polymers as main components of base oil; used oil feedstocks are derived from oils that are mechanically rubbed, degraded in lubrication performance by high temperatures.

Further, in the step (2), the kinematic viscosity of the used oil raw material should be lower than 180mP & s.

Further, in the step (2), the aqueous hydrogen peroxide solution accounts for 5-15% of the mass of the waste engine oil raw material.

Furthermore, for the used oil raw material with the acid value less than 4mg KOH/g or the dynamic viscosity more than 120 mPas, the mass concentration of the hydrogen peroxide water solution is 30-40%, and the reaction time is 1.5-2 h.

Furthermore, the reaction kettle is a steel-lined tetrafluoroethylene reaction kettle, and the stirring mode in the reaction kettle is spiral ribbon stirring.

Further, in the step (3), 1-2 filter screens are used during filtering, and the aperture of each filter screen is 100-200 meshes.

The invention has the beneficial effects that:

the raw material treated by the method is waste engine oil, and the waste engine oil is applied to the flotation of low-rank coal after being improved, so that the method has positive significance for the utilization and recovery of secondary resources. The chemical agent used in the method is mainly hydrogen peroxide, and the products of the treatment process are mainly water and precipitates and waste residues formed by oxidation. The method enables the used oil collecting agent to be cleaner to a certain extent, and no redundant pollutants are generated. The improved used oil collecting agent is more suitable for the flotation of low-rank coal slime. Can obtain high-yield and high-quality low-rank coal products.

Drawings

FIG. 1 is a flow chart of the method of the present invention.

Detailed Description

The present invention will be further described with reference to the following examples.

Example 1

Used oil and diesel and motor oil were sampled from petrol stations (brand 5W 30). The waste engine oil sample is subjected to oxidation treatment by the method. The acid value of this used oil sample was determined to be 3.73mg KOH/g and the kinematic viscosity was determined to be 115.32 mPas. First, an aqueous hydrogen peroxide solution was prepared at a mass concentration of 30%, and the pH was adjusted to 4.2 using a sodium hydroxide and sulfuric acid solution. Putting the prepared hydrogen peroxide aqueous solution and the used oil raw material into a reaction kettle, controlling the reaction time to be 1h, controlling the reaction temperature to be below 40 ℃, and using 5% of the hydrogen peroxide aqueous solution based on the mass of the used oil raw material. Stirring is continuously carried out in the reaction kettle by using helical ribbon stirring. And after the reaction is finished, filtering by using a 1-channel 200-mesh filter screen to obtain the improved used oil collecting agent.

The waste engine oil, the diesel oil, the engine oil and the waste engine oil treated by the method are respectively used as collecting agents to carry out laboratory flotation tests on low-rank coal (lignite). The concentration of the flotation coal slurry is 100 g/L. The collector dose was 5 kg/t. The foaming agent uses secondary octanol, and the dosage is 600 g/t. And respectively filtering the obtained flotation clean coal and tail coal, drying, weighing and measuring ash. The test conditions and results are listed in table 1.

The kinematic viscosity of the engine oil, used oil, and used oil treated by this method was measured using a viscometer. The test conditions and results are listed in table 2.

TABLE 1

TABLE 2

Sample number	Name of medicament	Dynamic viscosity mPa. multidot.s (25 ℃ C.)
			1	Engine oil	111.17
2	Diesel oil	7.15
			3	Waste engine oil	115.32
4	Improved waste engine oil	56.85

As can be seen from table 1, the method for improving the used oil collector provided by the invention can effectively improve the ability of the used oil to recover low-rank coal, and improve the collecting property and selectivity of the used oil. Compared with the traditional hydrocarbon oil collecting agent and untreated waste engine oil, the waste engine oil improved by the method is used as the collecting agent, and the yield of clean coal products of low-rank coal is higher and the ash content is lower. Table 2 shows that the method effectively reduces the dynamic viscosity of the used oil, and shows that the contents of components such as colloid and solid in the used oil are reduced, and the dispersing performance is improved.

The above description is only a part of the embodiments of the present invention, and not intended to limit the present invention, and it will be apparent to those skilled in the art that several modifications and variations can be made without departing from the principle of the present invention, and these modifications and variations should be construed as the protection scope of the present invention.