CN112691791A

CN112691791A - Preparation method of stabilizing agent and flotation promoter for water-based coal slime collecting agent

Info

Publication number: CN112691791A
Application number: CN202011386203.0A
Authority: CN
Inventors: 梁峰; 张晓丽; 王军; 梁亚丽; 路永广; 杨胜杰; 张超; 张国立
Original assignee: Henan Hezong Nenghua Technology Co Ltd; Henan Province Science And Technology Dev Co ltd
Current assignee: Henan Hezong Nenghua Technology Co Ltd; Henan Province Science And Technology Dev Co ltd
Priority date: 2020-12-02
Filing date: 2020-12-02
Publication date: 2021-04-23
Anticipated expiration: 2040-12-02
Also published as: CN112691791B

Abstract

The invention provides a preparation method of a stabilizing agent and a flotation promoter for a water-based coal slime collecting agent, which takes phthalic anhydride and glycol as raw materials and sodium dodecyl benzene sulfonate as a catalyst, controls reaction conditions for reaction, and adjusts the pH value of a product after the reaction to be 7-8 to obtain a final product. The reaction temperature is relatively low and is 120-130 ℃, the reaction temperature is normal pressure, no solvent is used, purification is not needed, the prepared product has three advantages in the using process, the dosage of the surfactant in the emulsification process is small, the stability of the prepared emulsification system is good, the oil saving rate of the prepared water-based collecting agent can reach 70%, and the process for producing the water-based coal slime collecting agent by using the product is simple and low in cost.

Description

Preparation method of stabilizing agent and flotation promoter for water-based coal slime collecting agent

Technical Field

The invention relates to the field of water-based coal slime collecting agents, in particular to a stabilizing agent and a flotation promoter for the water-based coal slime collecting agent and a preparation method of the stabilizing agent and the flotation promoter.

Background

Compared with petroleum and natural gas, the pollution caused by coal use is larger, but the national situation of the poor oil and the rich coal in China determines that the coal is still the main source of the energy in China in the next decades. At present, coal washing is still the most effective way for improving the quality of coal and reducing the sulfur content and ash content, and is the premise and the basis for clean and efficient utilization of coal. The flotation reagent is an essential additive in the coal washing process and is directly related to the quality and yield of clean coal. The flotation agent is divided into a collecting agent and a foaming agent, wherein the collecting agent is mainly nonpolar hydrocarbon oil such as kerosene, diesel oil and the like, the oil has extremely good hydrophobicity and is difficult to disperse in water, and the oil only exists in ore pulp in the form of large oil drops, so that the effective utilization rate of the oil is extremely low. In recent years, researchers emulsify hydrocarbon oil to prepare the water-based collecting agent greatly improve the utilization efficiency of the hydrocarbon oil, but the application range of the water-based collecting agent is limited due to the problems of large using amount of a surfactant, unstable emulsifying system, limited actual oil saving rate and the like during emulsification of the hydrocarbon oil.

Disclosure of Invention

The invention provides a stabilizing agent and a flotation promoter for a water-based coal slime collecting agent and a preparation method thereof, and the additive solves the problems of large using amount of an emulsifier, poor stability, poor flotation effect and the like of the water-based coal slime collecting agent, so that the water-based collecting agent can better exert the advantages of the water-based coal slime collecting agent and replace the traditional hydrocarbon oil collecting agent.

The technical scheme for realizing the invention is as follows:

a process for preparing the stabilizer and floatation promoter for the water-base coal slurry collector includes such steps as using phthalic anhydride and ethanediol as raw materials, sodium dodecylbenzenesulfonate as catalyst, controlling reaction condition, and regulating pH value to 7-8.

The mass ratio of phthalic anhydride, glycol and sodium dodecyl benzene sulfonate is 1 (1-3) to 0.05-0.1.

The reaction temperature is 120-130 ℃, and the reaction time is 4 h.

The pH value of the product after the reaction is adjusted to 7-8 by using 1 percent sodium hydroxide solution.

The invention has the beneficial effects that: the reaction temperature is relatively low and is 120-130 ℃, the reaction temperature is normal pressure, no solvent is used, purification is not needed, the prepared product has three advantages in the using process, the dosage of the surfactant in the emulsification process is small, the stability of the prepared emulsification system is good, the oil saving rate of the prepared water-based collecting agent can reach 70%, and the process for producing the water-based coal slime collecting agent by using the product is simple and low in cost.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.

Examples 1 to 3

The preparation method of the stabilizing agent and the flotation accelerant for the water-based coal slime collecting agent comprises the following steps:

mixing phthalic anhydride (A) and ethylene glycol (B) according to the mass ratio of 1:1, 1:2 and 1:3 respectively, adding catalyst sodium dodecyl benzene sulfonate (C), stirring and heating the mixture at the mass ratio of 1:0.05, continuing stirring and reacting for four hours when the temperature reaches 120 ℃, and neutralizing the mixture to the pH value of 7-8 by using 1% sodium hydroxide solution to obtain a final product and preparing a water-based collecting agent product with the diesel oil mass fraction of 50%.

The product performance mainly comprises the dosage of a stabilizer when the water-based collector is prepared, the stabilization time of the water-based collector product, the viscosity of the water-based collector product and the medicament consumption of the water-based collector product during flotation.

The preparation process of the water-based collecting agent comprises the steps of weighing 1-2g of the stabilizer prepared by the patent, placing the stabilizer in a beaker, slowly adding metered mineral oil (kerosene, diesel oil or other hydrocarbon oil), after the addition is finished, enabling the system to be sticky, adding metered water twice, adding 1/3 of the metered water for the first time, stirring for 20 minutes, adding 2/3 of the metered water, and continuing stirring for 20 minutes to obtain the water-based coal slime collecting agent product. The settling time of the water-based collector product was measured as the time when a 0.5mm aqueous phase appeared at the bottom.

The viscosity of the water-based collector product was measured using a commercially available rotational viscometer.

The product was tested for properties and the data are shown in table 1.

Table 1 examples 1-3 basic product properties

When the viscosity of the water-based collector product is too high, the pipe is easily blocked in the using process. According to our experience the product viscosity should be below 40mpa.s and the product prepared in example 3 produces a water based collector product with a high viscosity, probably due to the thickening effect of the high degree of polymerization of the product on the water based product under the process conditions.

Examples 4 to 6

mixing phthalic anhydride (A) and ethylene glycol (B) according to the mass ratio of 1:2, adding catalyst sodium dodecyl benzene sulfonate (C), stirring and heating the phthalic anhydride and the sodium dodecyl benzene sulfonate respectively according to the mass ratio of 1:0.05, 1:0.075 and 1:0.1, continuing stirring and reacting for four hours when the temperature reaches 120 ℃, neutralizing the pH value to 7-8 by using 1% sodium hydroxide solution to obtain a final product, and preparing a water-based collector product with the diesel oil mass fraction of 50%.

The product was tested for properties and the data are shown in table 2.

Table 2 examples 4-6 basic product properties

Under otherwise unchanged conditions, the amount of catalyst was varied and it can be seen from the table that as the amount of catalyst dodecylbenzene sulfonic acid increased, the product viscosity showed a tendency to increase and then decrease, but the settling time increased significantly.

Examples 7 to 9

mixing phthalic anhydride (A) and ethylene glycol (B) according to the mass ratio of 1:2, adding sodium dodecyl benzene sulfonate (C) serving as a catalyst, stirring and heating the mixture at the mass ratio of 1:0.1 of phthalic anhydride to sodium dodecyl benzene sulfonate respectively, continuously stirring and reacting for four hours when the temperature reaches 110 ℃, 115 ℃ and 120 ℃, and neutralizing the mixture to the pH value of 7-8 by using 1% sodium hydroxide solution to obtain a final product.

The product was tested for properties and the data are shown in table 3.

Table 3 basic properties of the products of examples 7 to 9

The preparation temperature was varied, without changing the other conditions, and it can be seen from the table that the product viscosity showed a tendency to decrease with decreasing temperature, with a significant decrease in the stabilization time. This may be caused by the reaction temperature being low and the reaction not being completely carried out.

In order to examine the use ratio, the oil saving rate and the flotation performance of the product in the embodiment, water-based collectors with different diesel oil contents are prepared by using products prepared at the reaction temperature of 120 ℃ when the ratio of the phthalic acid ester to the glycol is 1:2 and the ratio of the phthalic acid ester to the sodium dodecyl benzene sulfonate is 1:0.1, and the flotation indexes of the water-based collectors are tested. Wherein the foaming agent is sec-octanol, the dosage is 0.17 kg/ton coal slime, and the coal is coal slime with particle size below 0.5 mm.

The stability and viscosity of the water-based coal slime collecting agent prepared under the condition are basically in direct proportion to the using amount of the stabilizing agent, the stabilizing time is about 180 days, the viscosity does not exceed 30mpa.s, the water-based coal slime collecting agent is basically the best state of the product, and only the flotation effect is considered here, which is shown in table 4.

TABLE 4 flotation effect

It can be seen from table 4 that the flotation index of the water-based collector product produced by the patented product is almost equal to that of diesel oil when the oil content is 30%, and the flotation index also obviously increases with the increase of the additive dosage. The product not only has the function of stabilizing the water-based collecting agent, but also plays the role of a flotation promoter.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. A preparation method of a stabilizer and a flotation promoter for a water-based coal slime collecting agent is characterized by comprising the following steps: phthalic anhydride and ethylene glycol are used as raw materials, sodium dodecyl benzene sulfonate is used as a catalyst, reaction conditions are controlled for reaction, and the pH of a product after the reaction is adjusted to 7-8 to obtain a final product.

2. The preparation method of the stabilizing agent and the flotation promoter for the water-based coal slime collecting agent according to claim 1, characterized by comprising the following steps: the mass ratio of phthalic anhydride, glycol and sodium dodecyl benzene sulfonate is 1 (1-3) to 0.05-0.1.

3. The preparation method of the stabilizing agent and the flotation promoter for the water-based coal slime collecting agent according to claim 1, characterized by comprising the following steps: the reaction temperature is 120-130 ℃, and the reaction time is 4 h.

4. The preparation method of the stabilizing agent and the flotation promoter for the water-based coal slime collecting agent according to claim 1, characterized by comprising the following steps: the pH value of the product after the reaction is adjusted to 7-8 by using 1 percent sodium hydroxide solution.

5. The stabilizer and the flotation promoter for the water-based coal slime collector prepared by the method of any one of claims 1 to 4.