JPH01256591A - Bulk density improver of charge coal for production of coke - Google Patents

Abstract

PURPOSE:To improve the packing density of charge coal in a coke oven, by incorporating a particular anionic surfactant. CONSTITUTION:1-7wt.% anionic surfactant (A) which is a POE (1-4) alkyl ether sulfate salt, said salt being that of K, Na, NH4 or an alkanolamine such as mono-, di- or triethanolamine, 0.01-1wt.% nonionic or anionic fluorinated surfactant (B) having in its molecule a long-chain fluoroalkyl group (e.g., polyoxy-N-n-propyl-N-perfluorooctanesulfonamide) and 93-99wt.% nonionic surfactant (C) comprising a POE (7-14) alkyl ether are mixed together, thereby preparing a bulk density improver. 20-1,000ppm of the obtained improver is added to a charge coal having a grain size of up to 1mm.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a treatment agent for improving the packing density of raw coal in a coke oven when producing coke in a steelworks or the like.

(Prior art) - In general, it goes without saying that quality such as coke strength is significantly affected by the selection of coal type and blending ratio charged into a coke oven, and there are other factors as well. It is known that this can be improved by increasing the amount of charcoal (bulk density). Furthermore, by increasing the bulk density charged into the coke oven, the amount of carbonized gas can be reduced, resulting in energy savings, and the proportion of highly coking coal in coking coal can be reduced, resulting in lower coke prices. It is also expected that there will be benefits such as the ability to reduce emissions.

In order to improve the bulk density of coking coal in coke ovens,
Conventionally, steel works have attempted a so-called oiling method in which mineral oils such as A, B, and C heavy oils and waste oils, which are generated in large quantities at steel works, are added to coking coal and charged into a coke oven.

In addition, a method of adding a surfactant instead of the oiling method is disclosed in JP-A-58-11915 and JP-A-56-1.
It has been reported in Publication No. 00892, etc.

(Problem to be solved by the invention) The oiling method described above forms an oil film on the surface of coal particles to reduce friction between the coal particles and improve bulk density for coke ovens. The water content is 6~
Although it is effective to some extent when the ratio is small such as 8%, if the amount of oil added is 0.2 to 0.5% higher than the dry base of coking coal charged to the coke oven. Since it reaches as high as 0.8z, there is a risk of ignition in the transfer line, and there is also the problem of oil getting into the wastewater.Furthermore, since oil containing relatively high sulfur and nitrogen content is used, there is a risk of harmful gases and There are problems with the generation of irritating odors.

In addition, coking coal with a water content of over 8%, Special 1: 10 $
When oil is added to the above-mentioned coking coal, there are problems such as the bulk density of the coking coal charged into the coke oven does not improve and may even decrease.

On the other hand, the method of adding a surfactant lowers the surface tension of water adhering to the surface of coal particles to obtain lubricity between the coal particles, thereby increasing the bulk density to the coke oven. It is.

This method uses anionic surfactants as surfactants, especially alkylbenzene sulfonates such as dialkyl (anikenyl) sulfosuccinates and dodecylbenzene sulfonates, and is compared to the conventional oiling method. The same or higher bulk density improvement effect can be obtained.

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, fine particles with a particle size of 1 mm or less tend to account for more than 50%. However, such raw coals have drawbacks such as the fact that even when anionic surfactants such as those described above are used, the expected bulk density improvement effect cannot be obtained.

Therefore, in this invention, as a result of intensive research to find a surfactant that can improve the bulk density of raw coal that contains many fine particles, we have developed a surfactant that is composed of POE alkyl ether sulfate. It was discovered that anionic surfactants have a greater effect on bulk density than conventionally used anionic surfactants such as dialkyl (anikenyl) sulfosuccinates and dodecylbenzenesulfonates. .

(Means for Solving the Problems) Therefore, the present invention proposes a bulk density improver for raw coal for coke production, which contains an anionic surfactant composed of POE alkyl ether sulfate.

Here, the POE alkyl ether sulfate constituting the anionic surfactant is POE (1-4) alkyl ether sulfate, and its salts include K, Na,
Ntl, or alkanolamines such as mono-, di-, or triethanolamine are used, and such POE (1-4) alkyl ether sulfates include, for example, palm Examples include those synthesized using oils, fats and oils such as beef tallow and powdered whale oil, and synthetic alcohols such as Dopanol and Diatol.

The bulk density improver according to the present invention includes the above-mentioned POE.
(1-4) In addition to the alkyl ether sulfate, other nonionic or anionic surfactants may be added. According to research by the present inventors, it is particularly important to include long-chain fluoroalkyl groups in the molecule. By blending a nonionic or anionic fluorosurfactant with the above-mentioned POE alkyl ether sulfate alone, it is possible to further improve the bulk density.

Examples of such nonionic or anionic fluorosurfactants include boxoxy-N-n-propyl-ethanol C.I. F, 7302N (C1H?) (CH2C
H20) nH (n-10 to 20), N-n-propyl-
N-perfluorooctane sulfonamide CaF 1,s
OJH (Czll,), perfluorooctane sulfonic acid potassium salt CBF, , SO, K, same sodium kj
2 GaF+ySO3Na, ammonium salt c8F
．． S03NH4, N-n-propyl-N-perfluorooctanesulfonyl chrysine (C: +87) CH2CH2 former Potassium salt CaF
l? SO□N(C3H,)CH2C00K N -n
-7' mouth building N-perfluorooctane sulfamide ethyl phosphate C8F M7SOJ (C3H,)
C2H,0PO(Of-1) 2, N-n-propyl-
Also known as N-perfluorooctane sulfonamide ethyl sulfate.

Furthermore, the blending ratio of fluorosurfactant is POE (1 to 4)
The amount is 0.02 to IWt relative to the alkyl ether sulfate, and even if more than that is added, a larger bulk density improvement effect cannot be obtained, and it is not realistic from a cost standpoint.

On the other hand, according to the research of the present inventor, 50%
Particle size 1ao+ with a weight of 2 or more (mostly in terms of bulk)
For particle sizes below +, POE (7-14) alkyl ether, which is a nonionic surfactant, is more effective in improving the bulk density than anionic surfactants, and in particular, the above-mentioned POE alkyl ether sulfate is more effective than anionic surfactants. It has been found that by incorporating a salt, these nonionic surfactants can be made more effective in improving their bulk density.

Examples of the above-mentioned nonionic surfactants include those using synthetic alcohols such as dohanol and tayator, cetanol, and aliphatic alcohols of C1□ to CI4 as raw materials for the constituent alkyl groups.

In particular, when POE (7-14) alkyl ether is represented by the structural formula R-0-(toH2CI+.0) nH,
It is preferable that n is 7 to 14 and R is an alkyl group having 12 to 15 carbon atoms. POE alkyl ether having such a structure can be synthesized using, for example, a synthetic alcohol having 12 to 15 carbon atoms as a raw material.

As mentioned above, the blending ratio of POE (1 to 4) alkyl ether sulfate, which increases the bulk density improvement effect of nonionic surfactants, is 93 to 99 Wt of nonionic surfactants.
On the other hand, the formulation of PoE(1-4) alkyl ether sulfate is 1-7Wt! Even if the blending ratio of POE(1-4) alkyl ether sulfate is increased beyond this level, it will not contribute to the above-mentioned effect of improving the bulk density of the nonionic surfactant and is economically wasteful.

It should be noted that it is also possible to combine the above-mentioned fluorosurfactant and nonionic surfactant with the POE alkyl ether sulfate according to the present invention, or it is not possible to obtain a bulk density improvement effect superior to the combination of the above-mentioned two components. do not have.

In addition, when adding POE (1-4) alkyl ether sulfate or a mixture of POE (1-4) alkyl ether sulfate and POE alkyl ether to water or during storage of these solutions, does gelation occur? When ethylene glycol is added, POE(1-4) alkyl ether sulfate can be dissolved in water in a short time. Therefore, the chemical supply tank, supply piping, etc. can be more easily cleaned at the work site. In this case, the amount of ethylene glycol added is suitably 10 to 30 Wtl relative to POE (1-4) alkyl ether sulfate.

The amount of the bulk density improver according to the present invention may be about 20 ppm or more based on the dry amount of raw coal to be charged into the coke oven, and preferably 200 to 1 (lQ Oppa + is sufficient to improve bulk density). can get.

As for the addition method, the bulk density improver according to the present invention is added by spraying or the like, either alone or diluted with water as appropriate, to either the mixing or pulverizing of coking coal for coke production, or to the coking coal transfer line for charging into the furnace. I can list some methods.

As a special example, a sufficient effect can be obtained by suspending or dispersing it in oil, which corresponds to the conventional oiling method.

(Effects of the Invention) In summary, the present invention provides a POE (1-4) alkyl ether sulfate, and the salt thereof is Na.

N.H. or a bulk density improver for coking coal for coke production containing an anionic surfactant composed of alkanolamines such as mono-, di-, or triethanolamine, especially fine particles with a particle size of 1a+m or less. It is also effective in improving the bulk density of coking coal that contains many coal particles with a certain particle size.

Therefore, when using the treatment agent according to the present invention, the bulk density is always constant when coking coal containing a large amount of fine coal particles or low-quality low-to-slightly caking coal of poor quality is used. Therefore, coke can be produced under stable operating conditions.

In addition, when a nonionic or anionic fluorosurfactant having a long-chain fluoroalkyl group in the molecule is blended with the above-mentioned POE (1-4) alkyl needle sulfate, the anionic interface according to the present invention can be used. The effect can be further increased by increasing the bulk density of the active agent.

On the other hand, the anionic surfactant according to the present invention
(7-14) By blending an alkyl ether with a nonionic surfactant, it is possible to further increase the improvement in bulk density of coal particles having a relatively large particle size, which these nonionic surfactants have.

(Example) Examples of this invention will be shown below.

Example 1 Using the treatment agent of the present invention and the treatment agent of the comparative example for the following sample coals, the Kaza richness improvement effect was evaluated in the following manner.

Combination example t of the processing agent of the present invention POE (1) Combination example 2 with alkyl ether sulfuric acid POE (3) Combination example 3 with alkyl ether Nt acid Ni + 4 POE (4) Combination example 4 with alkyl ether sulfuric acid DE POE (2) Alkyl ether sulfuric acid S MEA blending example 5 POE (3) Alkyl ether sodium sulfate blending example 6 POE (3) Treatment agent comparative blending example 1 of argyl ether comparative example A heavy oil comparative blending example 2 P O E (12) Nonylphenol ether comparative blending example 3 P O E (1.4) Nonylphenol ether comparative formulation example 4 P O E (10) Oleic acid ester comparative formulation example 5 P O E (1.2) Sorbitan fatty acid ester comparative formulation example 6 P O E (12) Alkyl ether ( Product name 2
Nivicol BT-12) Comparative formulation example 7 POE (7) Alkyl ether (trade name Nivicol BT-7) Comparative formulation example 8 Dialkyl sulfosuccinate Judgment of the two effects on bulk density for the following sample coals It was carried out using the following method.

[Test charcoal] The charcoal to be tested was made of Canadian-produced charcoal, and was tested prior to the test.
Sieving, 6-3III11, 20 layers ff1%, 3-lf
fi+! , 40 weight, 1 m +++ or less 4 (2 weight) was used.

[Test method] Inner diameter 671111, outer diameter 72III11, height 500
From the upper end of a cylindrical stainless steel container A whose lower end is sealed, J.
0%, 12z sample coal (charcoal type: Intet single from Kanata) was added with the treatment agent of the present invention and the conventional treatment agent in the following proportions, and the mixture was evenly dropped and filled, and the surface was coated. Carefully level it out and read the filling height.

Next, using tapping device B as shown in Fig. 1, container A is lifted up to a height h (70 mm) and tapped five times, then the filling height is read and the bulk density is determined by dry-coal g/ It was calculated as a ccn3 value using the following formula.

This test was repeated three times and the average value of the bulk density was determined. Similar tests were also conducted on sample coals without the addition of treatment agents, and the average value of the bulk density was determined. The results are shown in Table 1 below.

Table 1 According to this, relatively good results were obtained for the blended coal that artificially contains many particles with a particle size of 1111111 or more, especially for various anionic POE alkyl ether sulfates.

Example 2 The bulk density improving effect of the following sample coals was evaluated using the same apparatus and method as in Example 1 using the treatment agent of the present invention and the treatment agent of the comparative example.

Processing agent blending example 7 of the present invention POE (3) Alkyl ether Na sulfate (trade name: Niracol NES203) Blend example 8 POE (12) Alkyl ether (trade name: :y:l-1kBT-12)
97Wt$POE (3) Sodium alkyl ether sulfate (Product name: Niracol NES20
3) (20 demons) 3Wt combination example 9 POE (+2) alkyl ether (product name: 2y:I-JkBT-12)
954VtXPOF, (3) Sodium alkyl ether sulfate (Product name: Niracol NES2
03) (20%) 5WtX formulation example 1
O POE (12) alkyl ether (trade name 22tcol BT-12)
90Wt$POE (3) Sodium alkyl ether sulfate (Product name: Ni:L NES203)
(20%) 10Wt$ Formulation Example 11 POE (12) Alkyl Ether (Product Name: Nilacol BT-12)
80Wt$POE (3) Sodium alkyl ether sulfate (Product name: Niracol NES20:1) (2
0%) 20Wt$ [Test charcoal Coal type A: Quintet from Kanata alone is sieved to a size of 3 mm or less prior to the test Coal type B: Quintet from Canada 6oz, Tramont from the United States 40% The mixed charcoal is sieved prior to testing: lam
The results of the following are shown in Table 2 below.

Table 2 As is clear from this, in the tests using both coal types A and B, good results were obtained by using Formulation Examples 8 to 11 in which POE (3) alkyl nitral sulfate and POE alkyl ether were blended. I got it.

Example 3 Using the same apparatus and method as in Example 1, the effect of improving bulk density was determined on the same test coal as in Example 2 using the treatment agent of the present invention and the treatment agent of the comparative example.

Processing agent formulation example 12 of the present invention POE (3) Alkyl ether (trade name: 2y:l-1kNES303) (30%)
Formulation example 13 POE (3) Alkyl ether sulfate TEA (Product name: 2Y+-L NES303) (30%)
99.97wt% fluorine-based surfactant [Product name: F-TOP 306A,% manufactured by Akita Kasei Co., Ltd.]
0.03111t% Blending example 14 POE (3) Alkyl ether sulfate TEA (Product name: Niracol NES3Q3) (30'X)
99.8WtX Fluorine-based interfacial surfactant C Product name: FTOP 3 [iA, manufactured by Shinshuyo Kasei Co., Ltd.]
0.2WU: Formulation Example 15 POE (3) Alkyl ether sulfate TEA (Product name::y:I-LE NEs:103) (30%)
99.591tX fluorine-based surfactant [Product name: FTOP 306A, manufactured by Shinshuyo Kasei Co., Ltd.]
o. swtx formulation example 16 POE (3) Alkyl ether sulfate TEA (Product name: Niracol NES303) (30%)
99.0Wtl fluorine-based interfacial surfactant [Product name: F-TOP 306A, manufactured by Shinshuyo Kasei Co., Ltd.] 1
．． 0wt% The results are shown in Table 3.

Table 3 As is clear from the results, good results were obtained in Formulation Examples 13 to 15 for the treatment agent containing POE alkyl ether sulfate TEA and a thread surfactant, but Formulation Example 16 clearly showed It was found that even if the blending ratio of the fluorosurfactant was increased, the bulk density improvement effect remained unchanged.

Example 4 The bulk density improving effect of the following sample coals was evaluated using the same apparatus and method as in Example 1 using the treatment agent of the present invention and the treatment agent of the comparative example.

Processing agent formulation example 17 of the present invention POE (3) Alkyl ether sulfate TEA (trade name: 2y:I-LE NEs303) (30%)
io weight 2POE (12) alkyl ether (Product name: -y:I-le BT-12)
90 weight 2 formulation example 18 POE (3) Alkyl ether sulfate TEA (Product name::y:I-1kNES303) (30%)
99.5% by weight fluorine surfactant [Product name: F-TOP 306A, manufactured by Shin-Akita Kasei Co., Ltd.] 0.5 weight 2 Comparative treatment agent comparative formulation example 9 Sodium dodecylbenzenesulfonate Comparative formulation example 10・2. Sodium hexyl sulfosuccinate comparative formulation example 11 poE(12) nonylphenol ether comparative formulation example 1
2 POE (12) Oleyl ether comparative blending example 13 POE (8) Octyl ether [Test coal] The blending ratio is approximately 45% Intet 252 from Canada, 45% from Australia (Collar, Turack water, Hoskisson, Moller, etc.) , Optimum 5z from South Africa, and 25% Tramont from the United States were used as test coals for coke production at an actual steel mill, and the coals were sieved prior to the test and those with a particle size of 3IIIL or less were used as test coals.

The results are shown in Table 4 below.

Table 4 As is clear from the results, when treated with the treatment agent of the present invention, anionic interfaces such as the previously proposed oil-link method, conventional dodecylbenzenesulfonate, and dialkyl sulfosucci salt-resistant A bulk density improvement effect superior to any of the methods in which an activator was added was obtained.

[Brief explanation of the drawing]

FIG. 1 is a side view showing a bulk density measuring method in an example. Patent applicant: Taihohe Gyo Co., Ltd.

Claims (3)

[Claims] (1) POE (1-4) alkyl ether sulfates, the salts of which contain anionic surfactants composed of K, Na, NH_4, or alkanolamines such as mono-, di-, or triethanolamine; A bulk density improver for coking coal for coke production. (2) Bulk density of raw coal for coke production according to claim 1, which contains 0.02 to 1% by weight of a nonionic or anionic fluorine surfactant having a long-chain fluoroalkyl group in the molecule. improver. (3) The bulk density improver for raw coal for coke production according to claim 1, which contains 93 to 99% by weight of a nonionic surfactant composed of POE(7-14) alkyl ether.