JPH02292391A - Treating agent for coking coal - Google Patents

Abstract

PURPOSE:To prevent a coking coal from clinging to equipment and improve the packing density of the coal by compounding a nonionic surfactant comprising a polyoxyethylene alkyl ether and a specific anionic surfactant into a coal oil. CONSTITUTION:A treating agent for a coking coal is prepd. by dissolving or dispersing 1 to 10% surfactant mixture contg. a nonionic surfactant comprising a polyoxyethylene alkyl ether of formula I (wherein R is 12 to 15C alkyl; and (n) is 3 to 9) obtd. by adding ethylene oxide to a higher alcohol having a 12 to 15C alkyl group and an anionic surfactant comprising a dialkyl sulfosuccinate of formula II (wherein R is alkyl; and M is Na or triethanolamine) or a polyoxyethylene alkyl ether sulfate of formula III (wherein R is 12 to 14C alkyl; and M is Na or triethanolamine) in a ratio of the nonionic to the anionic surfactant of 0.5 to 2.5 in a coal oil comprising a by-product oil (e.g. carbolic oil) which is obtd. in the carbonization of coal and contains an initial fraction of 130 deg.C or higher. The prepd. treating agent is added to the coking coal in an amt. of 0.3wt.% or lower based on the coal.

Description

[Detailed Description of the Invention] Industrial Application Fields The present invention is useful for preventing coking coal from adhering to hoppers, etc. when charging coking coal into a coke oven during coke production in steel plants, etc. This article relates to processing agents used to improve the packing density in coke ovens. <Prior art> It has long been known that the strength and other qualities of coke vary depending on the type of coal blended and drying conditions, but can also be improved by increasing the amount of coking coal charged into the coke oven. It is being done. However, recently there has been a tendency to use coking coal with a high blending ratio of non-caking coal, but when trying to increase the amount of coking coal charged to the coke oven, it is difficult to use the hopper during transfer. Various problems occur, such as blockage of coal, adhesion in handling equipment such as belt conveyors, coal falling from belt conveyors, and lack of bulk density in coke ovens.
In particular, when the moisture content of coking coal is high, the frictional force increases due to the surface tension of the moisture adhering to the surface of the coal particles, making it difficult for the coal particles to slip.This causes bridging during charging into the coke oven. etc., resulting in a decrease in bulk density. Therefore, in order to increase the amount of coking coal charged into the coke oven, steelworks have traditionally used A. B. The so-called oiling method is adopted, in which mineral oil such as C heavy oil or waste oil, which is generated in large quantities at steel mills, is added to coking coal. Further, methods of adding a surfactant instead of mineral oil are disclosed, for example, in JP-A-58-11915 and JP-A-56-1999.
This is reported in Publication No. 110892, etc. <Problems to be Solved by the Invention> However, the above-mentioned oiling method reduces friction between coal particles by forming an oil film on the surface of the coal particles, and when the moisture content of coking coal is 6 to 8%, However, since the amount added reaches 0.3 to 0.8% on a dry base of coking coal charged to the coke oven, there is a risk of ignition in the transfer line. Adding mineral oil to wastewater causes problems such as clogging of hoppers and increased adhesion to conveyor belts, and even lowering the bulk density of coking coal charged to coke ovens. On the other hand, the method of adding a surfactant instead of mineral oil obtains a lubricating effect between coal particles by lowering the surface tension of the water adhering to the surface of the coal particles, which improves the handling of hoppers, belt conveyors, etc. This is intended to prevent adhesion in equipment and improve bulk density in coke ovens. In this method, anionic surfactants such as dialkyl (alkenyl) sulfosuccinates, polyoxyethylene
7-14) Alkyl ether, polyoxyethylene (
7-14) The use of nonionic surfactants such as alkylphenol ethers has been practiced. Of these, methods that use dialkyl sulfosuccinates as surfactants are more effective than the conventional oiling method. However, in recent years, many attempts have been made to mix as much slightly coking coal as possible into the coking coal charged to coke ovens, and as a result, as much as 50% of the coking coal charged into coke ovens is made up of fine particles with a particle size of less than 100 yen. There is a tendency for coking coal such as
Anionic surfactants have the disadvantage that they do not have the expected bulk-density-improving effect. For example, 50% of particles are small particles with a particle size of less than 1 intestine.
Experimental results have also been reported showing that anionic surfactants are inferior to the above-mentioned nonionic surfactants in improving the bulk density of coking coal. Therefore, there has been a desire for a treatment agent that can provide a sufficient bulk density improvement effect even for raw coal containing a large amount of fine particles with a particle size of 1 mm or less. <<Means for Solving the Problems>> The present invention was proposed in view of the above, and uses a nonionic surfactant in which the alkyl group has 12 to 15 carbon atoms,
One or more polyoxyethylene alkyl ethers having an added mole number of ethylene oxide of 3 to 9, and an anionic surfactant such as dialkyl sulfosuccinic acid sodium salt or triethanolamine salt, and an alkyl group having 12 carbon atoms. -14 and the number of added moles of ethylene oxide is 2 to 4. Polyoxyethylene alkyl ether sulfate sodium salt or triethanolamine salt and the initial fraction produced during coal carbonization as coal oil are 130 ° C.
The above-mentioned by-product oil, and a treatment agent for raw coal for coke production, characterized in that the ratio of the nonionic surfactant to the anionic surfactant is 0.5 to 2.5. be. As the above-mentioned nonionic surfactant, one or more types of polyoxyethylene alkyl ethers, which are obtained by adding ethylene oxide to a higher alcohol whose alkyl group has 12 to 15 carbon atoms and are represented by the following formula, are used. ．． a-o- (C*LO) a-H (However, R is an alkyl group having 12 to 15 carbon atoms, and n is
3 to 9. ) In addition, as the anionic surfactant, dialkyl sulfosuccinates represented by the following formulas, R-0-COCHI R-0-COCH-30314 (where R is an alkyl group and M is an alkyl group and Na is triethanolamine) ) or one or more polyoxyethylene alkyl ether sulfates represented by the following formula are used. R-0- (C
．． H. O). -QSO self-praise (however, R has 12 or more carbon atoms)
14 alkyl group, M is Na or triethanolamine. ) Further, examples of by-product oils whose first distillate fraction is 130°C or higher during the above-mentioned coal carbonization include carbol oil, absorption oil, and creosote oil. In addition, the ratio of the nonionic surfactant to the anionic surfactant described above has a high density improvement effect in the range of 0.5 to 2.5. If the ratio is 0.5 or less, the above surfactant is There are problems with stability when blended with coal; 2.
When the value exceeds 5, the bulk density improvement effect decreases. The surfactants mentioned above are generally added at 1-10% in coal oil.
Dissolve or suspend to some extent and use as a processing agent. Further, the amount of the treatment agent of the present invention added to the raw coal should be 0.3% by weight or less. No problem occurs even if the amount is increased to 0.5% by weight. In addition, coal oil has a strong affinity for coking coal, can be recycled, and the cost of oil can be significantly reduced, making it very effective. Furthermore, as mentioned above, in the processing agent of the present invention, the amount of processing agent added can be significantly reduced compared to the conventional oiling method, so that the drawbacks of the conventional oiling method as described above can be improved. Can be done. The above-mentioned treatment agent may be added to the coking coal in any of the transfer lines such as mixing, pulverizing, or charging the coking coal into a furnace. Or, after adjusting the treatment agent by suspending it, add it by spraying, etc. As long as the treatment agent of the present invention satisfies the above-mentioned structural conditions, even if it is added to raw coal containing a large amount of fine particles with a particle size of 100 mL or less, it will not lubricate the particles. It can provide a sufficient bulk density improvement effect. Effects of the Invention As explained above, the effect of improving bulk density can be obtained simply by adding the treatment agent of the present invention to raw coal. Compared to conventional treatment agents, a significantly higher bulk density improvement effect can be obtained even for raw coal contained in the treatment agent. In addition, raw coal treated with the treatment agent of the present invention does not take up much space during storage, and has great advantages in terms of handling. In addition, since only a small amount is needed compared to processing agents,
It is economically advantageous, and the risk of ignition is significantly lower than when using conventional mineral oil. Therefore, by using the processing agent according to the present invention, stable operating conditions can be maintained at all times when using coking coal containing a large amount of fine coal particles or low-grade and slightly caking coal of poor quality. Coke can be produced. <Examples> Examples of the present invention will be shown below. Formulation example l Polyoxyethylene (7) cetanol ether
7 The number within 0 below wt% represents the number of moles of ethylene oxide added.
3 wt% carbol oil
90 wt% blending example 2 polyoxyethylene (7) F banol ether
7 wt% polyolefin ethylene (3) F banol Sodium sulfate
3 wt% carpol oil
90% %Blend Example 3 Polyoxyethylene《F》hetatanol ether
7 Sodium succinate A
3 wt% absorbed oil
92. 98wt% blending example 4 polyoxyethylene (5) secnor ether
4 wt% dioctyl sodium sulfur
6 wt% absorbed oil
90 wt% blending example 5 Polyolefin ethylene (7) Secnor ether
2 wt% dioctyl sodium succinate
4 wt% absorbed oil
94 wt% blending example 6 polyoxyethylene (5) cetanol ether
5 wt%5 lyoxyethylene《3》F banol Sodium sulfate
5 wt% carbol oil
90 wt% blending example 7 Kolioxyethylene《7》cetanol ether
3 wt% Waoctil Surunekoyaku [｝Riu▲
2 wt% absorbed oil
90 wt% blending example 8 polyoxyethylene <<5>> cetanol 1-tel
3 Affected % dioctyl sodium sulne succinate
7 wt% decrystallized anthracene oil
90 wt% Using the processing agents of Formulation Examples 1 to 8 that satisfy the constitutional conditions of the present invention described above, the evaluation tests shown below were conducted, and in each test, the system using the above processing agent was used as an example.
Furthermore, as comparative examples, treating agents such as surfactants and coal oil were similarly tested and are listed in each table.

[Evaluation test] ■Lubricity (l) In order to investigate the lubricity between coal particles, we created a hopper as shown in Figure 1, assuming an on-site device, and conducted a test to determine the degree of blockage. ．． The stainless steel device with 3 walls and 1 wall is each attached to a fixed A. It is composed of three parts, B and C. Part A has an inner diameter of 130mm x 130a
m, a cylinder with a height of 150+as, and a wall thickness of 1a+ at the bottom.
The stainless steel plate +w serves as shutter 1. In addition, part B is a hopper, and the lower outlet part has an inner diameter of 50svX
The size is 50mm. Section C is a box-shaped container with an inner diameter of 130 mm x 130 sm and a height of 150 m. First, in eight parts, add 2 pieces of hydrated sample charcoal equivalent to 700g dry weight.
Filled with (bulk density approximately 0.600 ””゜””1g/cI1
''), the bottom shutter 1 was pulled out at once, and the sample coal 2 in the 8th section was dropped into the B section.
The weight of the sample coal 2 that passed through the hopper and flowed out from the lower mouth to section C was measured, and the passage rate was calculated, which was used as a lubricity evaluation standard. The type of charcoal used was Quintet from Canada, which was sieved to 3 gardens or less. The results are shown in Table 1. ■Lubricity (Part 2) The same test as for ■Lubricity above was conducted. However, in this test, the sample coal supplied to Yabu had a bulk density of 047
0w*t. csat, 7c, s). The results are shown in Table 2. Table 1 (■Lubricity 1) Table 1 (■Lubricity 2) From Table 1, Examples 1 to 7 that satisfy the constitutional conditions of the present invention
In Comparative Example 1-10, the passage rate through the hopper was approximately 90% or more in any case where the moisture content was 8 to 14%. Not too much. Table 2 also shows the same results as above, and there is a clear difference in the passage rate values between Examples 1 to 3 of the present invention and Comparative Examples 1 to 6. In other words, it can be seen that the coal particles to which the treatment agent of the present invention was added had an extremely high passage rate in this test compared to those using the conventional treatment agent. Therefore, from the above results,
The treatment agent of the present invention provides extremely high lubricity between coal particles compared to conventional treatment agents, and the coal particles to which the treatment agent of the present invention is added apparently have excellent fluidity. It can also be said that it is granted. ■Slippery stainless steel plate (70-■X 150saX 1 adjustment)
We created a device (Figures 2 and 3) in which the inclination increases at a rate of 3°/see with 3 as the fulcrum on the short side. A predetermined amount of water was added to a completely dried Canadian quintet with a size under 10 mesh, and after thorough mixing, a treatment agent was added and mixed again. 5g of the sample charcoal adjusted in this way was placed in the center of the stainless steel plate with a load of 1kg on an area of 6csXJc garden! It was compacted and molded for minutes. Then, the motor 5 was operated and the stainless steel plate 3 was gradually tilted at a low speed, and the inclination angle of the stainless steel plate 3 when the sample coal 4 slipped toward the fulcrum was read and the result was obtained. If the material is sliding strongly on the stainless steel plate, the sliding angle will be large, and if the sliding property is small, the sliding angle will be low.
On the contrary, this is an attempt to investigate slipperiness based on the magnitude of the slip angle. The results are shown in Table 3. Table (C) From Table 3, Examples 1 to 3 that satisfy the structural conditions of the present invention
It can be seen that in both cases of water content of 8% and 12%, the sample coal falls at an angle where the sliding angle is extremely low compared to Comparative Examples 1 to 8. That is, the treatment agent of the present invention provides extremely high lubricity between the sample coal particles compared to the conventional treatment agent, and thus reduces the slipperiness thereof. ■Bulk Density Measurement From above a cylindrical stainless steel container 6 with an inner diameter of 67 am and a height of 5001 cm, the bottom end of which is sealed, the dry weight is 700 g.
Equivalent water-containing test coal (charcoal type: Quintet single from Canada)
Let it fall and fill evenly, and carefully smooth the surface to make it flat.
The height h《
After lifting it up to 70 so 1 and tapping it 5 times, read the filling height and calculate the bulk density using the following formula.
The results are shown in Table 4. From Table 4, Examples 1 to 4 that satisfy the structural conditions of the present invention
The bulk density of Comparative Examples 1 to 7 was 0.0% in any case where the water content was 8 to 12%. 1~0. In other words, it can be seen that the processing agent of the present invention has an extremely high bulk density improving effect compared to conventional processing agents.

[Brief explanation of the drawing]

Fig. 1 is a longitudinal side view showing a method for measuring lubricity of a treatment agent of the present invention, Fig. 2 is a side view of a slipperiness measuring device, Fig. 3 is a plan view of the same, and Fig. 4 is a method for measuring bulk density. FIG.

Claims (1)

[Claims] As a nonionic surfactant, the alkyl group has 12 carbon atoms.
~15, and the number of added moles of ethylene oxide is 3~
9, one or more polyoxyethylene alkyl ethers, an anionic surfactant such as dialkyl sulfosuccinic acid sodium salt or triethanolamine salt, an alkyl group having 12 to 14 carbon atoms, and an added mole number of ethylene oxide. Polyoxyethylene alkyl ether sulfate sodium salt or triethanolamine salt which is 2 to 4 and the initial distillate produced during coal carbonization as coal oil is 130 ° C.
A treatment agent for raw coal for coke production, comprising the above-mentioned by-product oil, and characterized in that the ratio of the nonionic surfactant to the anionic surfactant is 0.5 to 2.5.