CN115106200B

CN115106200B - Coal dressing compound collector, preparation method thereof and coal slime flotation method

Info

Publication number: CN115106200B
Application number: CN202111240556.4A
Authority: CN
Inventors: 黄根; 徐佳琪; 江鹏; 王若彤
Original assignee: China University of Mining and Technology Beijing CUMTB
Current assignee: China University of Mining and Technology Beijing CUMTB
Priority date: 2021-10-25
Filing date: 2021-10-25
Publication date: 2024-06-21
Anticipated expiration: 2041-10-25
Also published as: CN115106200A

Abstract

The application provides a coal dressing compound collector, a preparation method thereof and a slime flotation method, wherein the coal dressing compound collector comprises the following raw materials in parts by weight: 50-80 parts of vegetable oil, 10-20 parts of alkane acid esters, 5-15 parts of aromatic acid esters and 5-15 parts of long-chain acid. According to the application, the vegetable oil, the alkane acid esters, the aromatic acid esters and the long-chain acid are compounded, the obtained compound collector contains both polar groups and nonpolar groups, the polar groups are adsorbed on oxygen-containing sites on coal particles, and the nonpolar groups are adsorbed on hydrophobic sites on the surface of low-rank coal, so that the flotation effect of coal slime is effectively improved; moreover, under the condition of similar ash content, the yield of the clean coal can be greatly improved, the efficient utilization of the coal slime is facilitated, and the economic benefit is improved.

Description

Coal dressing compound collector, preparation method thereof and coal slime flotation method

Technical Field

The application relates to the technical field of coal dressing, in particular to a coal dressing compound collector, a preparation method thereof and a slime flotation method.

Background

Along with the development of large-scale coal preparation machinery and exploitation of high-quality coal resources, the content of coal slime in raw coal is increased. Flotation is particularly important in upgrading coal slime. Flotation is widely used in fine coal separation, and froth flotation is an effective method for separating fine particles by chemical and mechanical adjustment according to the natural hydrophobicity difference among the particles. Typical flotation agents for flotation are collectors, frothers, etc.

At present, the collector commonly used for coal dressing is nonpolar hydrocarbon oil such as kerosene, diesel oil and the like. The nonpolar hydrocarbon oil can be adsorbed on the surface of coal particles as a collector to enhance hydrophobicity, so that clean coal and gangue are separated. However, nonpolar hydrocarbon oils such as diesel and kerosene have a relatively small molecular weight and are easily lost in the pores of the coal, so that the dosage of the agent is relatively large. In the coal preparation and flotation, the dosage of the nonpolar hydrocarbon oil collector is generally 1-4kg/1t coal slime, and petrochemical products such as diesel oil and kerosene are not renewable. The excessive consumption of the collector in the flotation process can cause extremely waste of resources, so that the search for the efficient environment-friendly collector is a development trend of improving the coal slime flotation effect at present.

Disclosure of Invention

The application aims to provide the compound collecting agent for the clean coal, the preparation method thereof and the coal slime flotation method, wherein the compound collecting agent is environment-friendly, high in safety, low in cost and high in economic benefit, and can remarkably improve the flotation effect of the coal slime and the collection performance of the clean coal.

In order to achieve the above object, the present invention provides the following technical solutions:

The coal dressing compound collector comprises the following raw materials in parts by weight: 50-80 parts of vegetable oil, 10-20 parts of alkane acid esters, 5-15 parts of aromatic acid esters and 5-15 parts of long-chain acid.

In some embodiments, the vegetable oil comprises at least one of rice bran oil, peanut oil, shea butter, and jojoba oil.

In some embodiments, the paraffinic esters comprise at least one of methyl laurate, methyl myristate, and methyl palmitate.

In some embodiments, the aromatic acid esters include at least one of diethyl phthalate, dibutyl phthalate, and dihexyl phthalate.

In some embodiments, the long chain acid comprises at least one of oleic acid and linoleic acid.

The application also provides a preparation method of the coal dressing compound collector, which comprises the following steps: mixing the raw materials uniformly.

The application also provides a coal slime flotation method, which comprises the steps of mixing raw materials including coal slime pulp, a coal dressing compound collector and a foaming agent, forming foam, and scraping the foam to obtain clean coal;

the coal dressing compound collector is the coal dressing compound collector.

In some embodiments, the process of mixing the raw materials including the coal slurry, the beneficiation complex collector, and the frother comprises:

Firstly adding the coal dressing compound collector into the coal slime pulp, and uniformly mixing; then adding the foaming agent and mixing uniformly.

In some embodiments, the concentration of the coal slurry is 40-100g/L.

In some embodiments, 1-5kg of the combined collector is used per ton of coal slurry.

In some embodiments, 50-100g of the frother is used per ton of coal slurry.

In some embodiments, the time for scraping the foam is 3-5 minutes.

The application has the beneficial effects that:

according to the application, the vegetable oil is used for replacing diesel oil or kerosene, fossil resources can be saved, and the vegetable oil is renewable, environment-friendly, high in safety and low in price, and has good economic and environmental benefits; the vegetable oil, the alkane acid esters, the aromatic acid esters and the long-chain acid are compounded, the obtained compound collector contains polar groups and nonpolar groups, the polar groups are adsorbed on oxygen-containing sites on coal particles, and the nonpolar groups are adsorbed on hydrophobic sites on the surface of low-rank coal, so that the flotation effect of coal slime is effectively improved; moreover, under the condition of similar ash content, the yield of the clean coal can be greatly improved, the efficient utilization of the coal slime is facilitated, and the economic benefit is improved.

Detailed Description

The term as used herein:

"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.

The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.

When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.

In these examples, the parts and percentages are by mass unless otherwise indicated.

"Parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g, 2.689g, or the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. or the mass of the A component is aK, the mass of the B component is bK (K is any number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.

"And/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).

The application provides a coal dressing compound collector which comprises the following raw materials in parts by weight: 50-80 parts of vegetable oil, 10-20 parts of alkane acid esters, 5-15 parts of aromatic acid esters and 5-15 parts of long-chain acid.

Optionally, the vegetable oil can be used in the raw materials of the coal dressing compound collector in any one of 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts and 50-80 parts by weight; the amount of the alkane acid ester may be any one of 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, and 10 to 20 parts; the amount of the aromatic acid ester may be any one of 5 parts, 8 parts, 10 parts, 12 parts, 15 parts and 5 to 15 parts; the amount of the long-chain acid may be any one of 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, and 5 to 15 parts.

The vegetable oil is renewable, harmless to the environment and human bodies, safe and environment-friendly, and low in price compared with diesel oil and kerosene, and contains a large amount of fatty acid and stearic acid, and the carbon chains of the fatty acid and the stearic acid are long, so that the vegetable oil can provide polar groups and nonpolar groups simultaneously; polar groups and nonpolar groups also contained in the alkane acid esters and the aromatic acid esters; the polar groups can be combined with oxygen-containing functional groups on the surface of the low-rank coal, and the nonpolar groups can be combined with nonpolar surfaces on the surface of the low-rank coal, so that the floatability of the low-rank coal is improved.

According to the application, the vegetable oil is used for replacing diesel oil or kerosene, and is compounded with the alkane acid esters, the aromatic acid esters and the long-chain acid, so that the lightning and the ignition point of the obtained compound collector are higher than those of the diesel oil and the kerosene, and most importantly, the compound collector contains polar groups and nonpolar groups, the polar groups are adsorbed on oxygen-containing sites on coal particles, and the nonpolar groups are adsorbed on hydrophobic sites on the surface of low-rank coal, so that the flotation effect of coal slime is effectively improved; under the condition of similar ash content, the coal dressing compound collector can greatly improve the yield of clean coal, is beneficial to the efficient utilization of coal slime and improves the economic benefit.

In some embodiments, the paraffinic acid ester is at least one of methyl laurate, methyl myristate, and methyl palmitate.

In some embodiments, the aromatic acid ester is at least one of diethyl phthalate, dibutyl phthalate, and dihexyl phthalate.

The application also provides a preparation method of the coal dressing compound collector, which comprises the following steps: uniformly mixing the raw materials; preferably, the raw material components are mixed in an ultrasonic dispersion mode to obtain the golden and uniformly dispersed compound collector.

the coal dressing compound collector is the coal dressing compound collector.

The coal slime pulp is obtained by adding coal slime into a flotation tank, adding water, stirring and wetting, and the stirring time is about 2 minutes.

In some embodiments, the concentration of solids in the slurry is 40-100g/L, such as 40g/L, 100g/L, 50g/L, 60g/L, 70g/L, 80g/L, 90g/L, 100g/L, or the like.

In some embodiments, the amount of the built collector used per ton of coal slurry is 1-5kg. Such as 1kg, 2kg, 3kg, 4kg or 5kg, etc.

In some embodiments, the frother is used in an amount of 50-100g, such as 50g, 60g, 70g, 80g, 90g, 100g, etc., per ton of coal slurry.

In some embodiments, the time for scraping the foam is 3-5 minutes.

Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

Example 1

50 Parts of rice bran oil, 20 parts of methyl laurate, 5 parts of diethyl phthalate and 15 parts of oleic acid are taken and placed in a container, and are uniformly mixed in an ultrasonic dispersion mode, so that the compound collector is obtained.

Example 2

60 Parts of rice bran oil, 12 parts of methyl laurate, 8 parts of diethyl phthalate and 12 parts of oleic acid are taken and placed in a container, and are uniformly mixed in an ultrasonic dispersion mode, so that the compound collector is obtained.

Example 3

Taking 70 parts of rice bran oil, 15 parts of methyl laurate, 10 parts of diethyl phthalate and 10 parts of oleic acid, placing the rice bran oil, the methyl laurate, the diethyl phthalate and the oleic acid in a container, and uniformly mixing the rice bran oil, the methyl laurate, the diethyl phthalate and the oleic acid in an ultrasonic dispersion mode to obtain the compound collector.

Example 4

50 Parts of rice bran oil, 12 parts of methyl laurate, 12 parts of diethyl phthalate and 8 parts of oleic acid are taken and placed in a container, and are uniformly mixed in an ultrasonic dispersion mode, so that the compound collector is obtained.

Example 5

80 Parts of rice bran oil, 10 parts of methyl laurate, 15 parts of diethyl phthalate and 5 parts of oleic acid are taken and placed in a container, and are uniformly mixed in an ultrasonic dispersion mode, so that the compound collector is obtained.

Comparative example 1

This comparative example 1 differs from example 1 in that: removing methyl laurate; otherwise, the same as in example 1 was conducted.

Comparative example 2

This comparative example 2 differs from example 1 in that: removing diethyl phthalate; otherwise, the same as in example 1 was conducted.

Comparative example 3

This comparative example 3 differs from example 1 in that: removing oleic acid; otherwise, the same as in example 1 was conducted.

Comparative example 4

This comparative example 4 differs from example 1 in that: replacing 50 parts of rice bran oil with 40 parts, and replacing 15 parts of oleic acid with 4 parts; otherwise, the same as in example 1 was conducted.

Comparative example 5

This comparative example 5 differs from example 1 in that: replacing 50 parts of rice bran oil with 90 parts, and replacing 15 parts of oleic acid with 17 parts; otherwise, the same as in example 1 was conducted.

1. The compound collectors prepared in examples 1 to 5 and comparative examples 1 to 5 and diesel oil are used as collectors, and flotation tests are respectively carried out on inner Mongolia flame coal, wherein the specific flotation method is as follows:

(1) Adding the coal slime into a flotation tank, adding water, stirring and wetting for 2min to obtain coal slime ore pulp with the concentration of 100 g/L.

(2) Adding a collecting agent into the coal slime pulp obtained in the step (1), wherein the amount of the collecting agent used for each ton of the coal slime pulp is 4kg; then stirring for 1min, adding a foaming agent, namely secondary octanol, wherein the amount of the foaming agent per ton of coal slime pulp is 100g, stirring to form stable foam, scraping the foam for 3min, and scraping out clean coal.

The results of the flotation test are shown in table 1 below.

Table 1 comparison of flotation effects of diesel and formulated collectors on long flame coals

Collector name	Yield of clean coal/%	Clean coal ash/%
			Diesel oil	25.79	14.48
The built collector of example 1	58.85	14.33
			The built collector of example 2	60.61	14.59
The built collector of example 3	57.62	14.21
			The built collector of example 4	55.23	14.15
The built collector of example 5	62.39	14.66
			Compound collector of comparative example 1	51.34	14.89
Compound collector of comparative example 2	53.16	14.66
			Compound collector of comparative example 3	50.44	14.84
Compound collector of comparative example 4	51.15	14.75
			Compound collector of comparative example 5	48.13	14.55

Compared with the compound collector prepared in the comparative example and directly using diesel oil as the collector, the compound collector prepared in the embodiment of the application has higher yield of clean coal under the same collector dosage when applied to long flame coal flotation.

2. The compound collectors prepared in examples 1-5 and comparative examples 1-5 and diesel oil are used as collectors, and flotation tests are respectively carried out on coking coals of a certain coal preparation plant in Shanxi, wherein the specific flotation method is as follows:

(1) Adding the coal slime into a flotation tank, adding water, stirring and wetting for 2min to obtain coal slime ore pulp with the concentration of 80 g/L.

(2) Adding a collector into the coal slime pulp obtained in the step (1), wherein the amount of the collector used for each ton of the coal slime pulp is 1.5kg; then stirring for 1min, adding a foaming agent, namely secondary octanol, wherein the amount of the foaming agent used for each ton of coal slime pulp is 80g, stirring, forming stable foam, scraping foam for 4min, and scraping clean coal.

The flotation test results are shown in table 2 below.

Table 2 comparison of flotation effects of diesel and formulated collectors on coking coals

Collector name	Yield of clean coal/%	Clean coal ash/%
			Diesel oil	76.74	15.59
The built collector of example 1	81.04	15.46
			The built collector of example 2	82.61	15.63
The built collector of example 3	80.49	15.06
			The built collector of example 4	80.99	15.39
The built collector of example 5	84.62	15.98
			Compound collector of comparative example 1	80.10	15.65
Compound collector of comparative example 2	79.28	15.39
			Compound collector of comparative example 3	78.15	14.54
Compound collector of comparative example 4	77.44	14.66
			Compound collector of comparative example 5	79.15	15.62

As can be seen from table 2 above, compared with the compound collector prepared in the comparative example and the direct use of diesel oil as the collector, the compound collector prepared in the embodiment of the application has higher yield of clean coal under the same collector dosage when applied to coking coal flotation.

3. The compound collectors prepared in examples 1-5 and comparative examples 1-5 and diesel oil are used as collectors to respectively carry out flotation tests on high-ash refractory coal of the Tangshan ores, and the specific flotation method is as follows:

(1) Adding the coal slime into a flotation tank, adding water, stirring and wetting for 2min to obtain coal slime ore pulp with the concentration of 60 g/L.

(2) Adding a collector into the coal slime pulp obtained in the step (1), wherein the amount of the collector used for each ton of the coal slime pulp is 1kg; then stirring for 1min, adding a foaming agent, namely secondary octanol, wherein the amount of the foaming agent per ton of coal slime pulp is 60g, stirring, forming stable foam, scraping foam for 5min, and scraping clean coal.

The flotation test results are shown in table 3 below.

Table 3 comparison table of flotation effect of diesel oil and compound collector on high ash refractory coal

Collector name	Yield of clean coal/%	Clean coal ash/%
			Diesel oil	67.37	14.33
The built collector of example 1	74.71	13.61
			The built collector of example 2	76.25	14.58
The built collector of example 3	73.26	13.55
			The built collector of example 4	72.52	13.36
The built collector of example 5	78.95	14.95
			Compound collector of comparative example 1	71.15	13.47
Compound collector of comparative example 2	70.43	13.62
			Compound collector of comparative example 3	68.05	13.56
Compound collector of comparative example 4	70.19	13.05
			Compound collector of comparative example 5	69.33	14.62

As can be seen from the above Table 3, the compound collector prepared in the embodiment of the application has higher yield of clean coal under the same collector dosage when being applied to flotation of high-ash refractory coal compared with the compound collector prepared in the comparative example and directly using diesel oil as the collector.

In the embodiment of the application, rice bran oil is replaced by the other vegetable oil, oleic acid is replaced by linoleic acid, methyl laurate is replaced by the other alkane acid esters, and diethyl phthalate is replaced by the other aromatic acid esters, so that when the prepared compound collector is applied to the coal slime flotation, the flotation effect is equivalent to that of the embodiment.

Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.

Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims

1. The coal dressing compound collector is characterized by comprising the following raw materials in parts by weight: 50-80 parts of vegetable oil, 10-20 parts of alkane acid esters, 5-15 parts of aromatic acid esters and 5-15 parts of long-chain acid;

The vegetable oil comprises at least one of rice bran oil, shea butter and jojoba oil;

The long-chain acid comprises at least one of oleic acid and linoleic acid;

The alkane acid esters comprise at least one of methyl laurate and methyl myristate;

the aromatic acid esters include at least one of diethyl phthalate, dibutyl phthalate and dihexyl phthalate.

2. A method for preparing a coal dressing compound collector, which is characterized in that the coal dressing compound collector is the coal dressing compound collector in claim 1; the preparation method comprises the following steps: mixing the raw materials uniformly.

3. The coal slime flotation method is characterized in that raw materials comprising coal slime pulp, a coal dressing compound collector and a foaming agent are mixed to form foam and then scraped to obtain clean coal;

The coal dressing compound collector is the coal dressing compound collector of claim 1.

4. A slime flotation process according to claim 3, characterized in that the process of mixing the raw materials comprising slime pulp, coal dressing complex collector and frother comprises:

5. A slime flotation process according to claim 3, characterized in that the concentration of the slime pulp is 40-100g/L.

6. A slime flotation process according to claim 3, characterized in that 1-5kg of the built collector is used per ton of the slime pulp.

7. A slime flotation process according to claim 3, characterized in that 50-100g of the frother is used per ton of the slime pulp.

8. A slime flotation process according to claim 3, characterized in that the scraping foam is being performed

The interval is 3-5min.