KR101253826B1

KR101253826B1 - Aqueous solution compound polyvinyl acetate preventing cokes specialization

Info

Publication number: KR101253826B1
Application number: KR1020100095829A
Authority: KR
Inventors: 이종환; 오진환
Original assignee: 오진환; 이종환
Priority date: 2010-10-01
Filing date: 2010-10-01
Publication date: 2013-04-12
Also published as: KR20120034346A

Abstract

The present invention relates to a method for producing a polyvinyl alcohol composite aqueous solution for preventing coke differentiation, and in particular, a polyvinyl alcohol composite aqueous solution containing an additive selected from the group consisting of polyvinyl alcohol and a surfactant. By maintaining the strength of coke properly in the blast furnace, it promotes breathability and combustibility, and another effect is to minimize the cracking phenomenon caused by physical collisions during coke transfer to improve the quality of coke, such as maintaining the coke particle size, and improve the coke yield. have.

Description

Aqueous solution compound polyvinyl acetate preventing cokes specialization

The present invention relates to a method for enhancing the effect by adjusting the particle size of the raw coal in metallurgical coke, and more specifically, by setting the crushing criteria as a relationship between the total inert of the raw coal and the maximum flow rate The present invention relates to the preparation of a polyvinyl alcohol (Polyvinyl acetate or less PVA) composite aqueous solution for preventing coke differentiation to adjust the particle size of raw coal.

In steel mills, coals obtained from coal mines are usually deposited in coal yards for each type of coal and discharged according to the usage plan.Then, the coal is crushed for each type of coal and stored in a mixing tank for each type of coal. Coke is charged into a coke oven through a reservoir and dried for 17 to 20 hours to produce coke.

In particular, when importing coal raw materials from abroad, coke is manufactured by mixing about 8 ~ 12 kinds of coal.In this case, the particle size of the blended coal is generally 3mm or less so that the particle size is 80% to 90%. It manages granularity. However, when crushing in batches without considering the crushing granularity according to the type of coal as described above, coking coal, which is a metallurgical coal, loses coking capacity due to over or under crushing depending on the characteristics of the coal. There is a problem that can not properly exhibit the caking ability during the drying.

As a method for adjusting the particle size of the general raw material coal, a method of adjusting the particle size after controlling the crusher hammer while passing the raw material coal through the crusher, crushing the coal and confirming the coal particle size before and after crushing is performed. However, the particle size adjusting method does not have good crushing when the moisture is high according to the moisture content of coal, and there is a problem such as productivity decrease because it takes a long time to analyze. In addition, the coke produced in the coke oven is a coke having a certain size of particle size that can be used in the furnace, but it must be granulated in the furnace, but it is crushed in the long-distance transport process is a major cause of problems in the production of molten iron in the furnace.

In the prior art, the application number 10-2004-0028454 relates to a method for producing high-strength coke by controlling the size of the inner tinite present in the coal by crushing and blending coal with the method for producing high-strength coke. Separately crushing the various brands or types of coal such that the cumulative volume of crude inertite is below the reference value, and crushing the coal directly into the coke oven, or the crushed coal of at least one other brand or type. It is composed of a step of charging after combining with pulverized / pulverized coal.

In addition, Application No. 10-2008-0021919 relates to a method for producing metallurgical coke, and pressurizes the raw coal, which is composed of bituminous coal such as bituminous coal, anthracite coal, powdered coke and powdered coal, to a pressure of 50 kg / cm 2 or more to briquettes ( In the method of manufacturing metallurgical coke for carbonizing briquettes into briquettes, the raw coal is charged into each carbonization chamber of a disk-shaped rotary furnace equipped with a plurality of carbonization chambers and preheated according to the rotation of the rotary furnaces. Dehydration and preheating, reaction, aging and cooling by furnace cooling and air cooling in each zone divided into reaction zone, aging zone and cooling zone, and the respective preheat zone, reaction zone, aging zone and cooling zone By designating a location and placing a temperature measuring instrument therein, it compares the planned temperature with the measured temperature to control the temperature, discharges the dried product after cooling and stores it as necessary. Through a number of robo in order for the dry distillation operation to down again to the raw carbon contents to progress to be completed.

As described above, there is a development of technology such as increasing coke strength by adding an additive to coal, but there is a lack of development of a technology for improving strength or differentiating coke by modifying the produced coke itself. .

The present invention is to solve the problems of the prior art as described above, and to provide a PVA composite aqueous solution as a coke reinforcement that can improve the yield by directly spraying the coke to improve the appropriate cold strength and improve the fraction It is done.

The present invention as a technical idea for achieving the above object,

Polyvinyl alcohol (PVA) resin as a main component, characterized in that consisting of a surfactant and preservatives mixed with water and used.

4.994 to 5 parts by weight of the polyvinyl alcohol resin, 0.005 to 1 part by weight of the surfactant, and 0.001 to 0.2 parts by weight of the isocyazoline-based compound as the preservative, and 93.75 to 95 parts by weight of water. It is characterized by.

The polyvinyl alcohol resin has an average saponification degree of 65 to 97 mol% and an average degree of polymerization of 200 to 3000.

The surfactant is a polyoxyethylene-based, and isocyanoline-based compound is added as a preservative.

The polyoxyethylene surfactant is M-TDE1020, characterized in that the isocyazoline-based preservatives are Betacide.

According to the present invention, by spraying the coke-reinforced PVA composite aqueous solution to the produced coke to maintain the strength of the coke properly in the blast furnace to promote the breathability and combustibility, the differentiation that may occur during the movement of coke (broken phenomenon) It is possible to minimize, thereby increasing the quality of the coke and to improve the yield of the coke is an effective invention.

1 is a perspective view showing a conventional coke
2 is a perspective view showing a preferred embodiment of the present invention.
3 is a cross-sectional view showing an enlargement of the inventor a

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.

1 is a perspective view showing a conventional coke, Figure 2 is a perspective view showing a preferred embodiment of the present invention, Figure 3 is a cross-sectional view showing an enlarged view of the present inventor a.

In the present invention, the saponification degree is 0.005 to 1 part by weight of polyoxyethylene compound as surfactant, 0.001 to 0.2 part by weight of isocyazoline compound as preservative, and water content of 4.994 to 5 parts by weight of polyvinyl alcohol resin of 65 to 97 mol%. It is composed of a polyvinyl alcohol composite aqueous solution containing 93.75 ~ 95 parts by weight to prepare and use.

Referring to the action according to the polyvinyl alcohol composite aqueous solution to prevent coke differentiation of the present invention configured as described above are as follows.

The present invention provides a polyvinyl alcohol composite aqueous solution (20) containing a plasticizer, a surfactant, and a preservative in a polyvinyl alcohol resin in order to increase the appropriate level (DI value) of the coke (10) and in particular improve the fraction of the coke (10). ) To spray on.

The polyvinyl alcohol composite aqueous solution 20 of the present invention contains a polyvinyl alcohol resin as a main component and is obtained by neutralizing a vinyl ester compound and saponifying a vinyl ester polymer obtained. As said vinyl ester type compound, vinyl formate, vinyl acetate, a vinyl triiole acetate, a vinyl formate, vinyl laurate, a vinyl paritate, a vinyl stearate, etc. are used individually or in mixture, but vinyl acetate is suitable for practical use. Do.

In the present invention, other monomers may be copolymerized within the scope of not impairing the object of the present invention. Examples of the monomer include, for example, olefins such as ethylene, propylene, isobutylene, acrylic acid, methacrylic acid, crotonic acid, Maleic acid, itaconic acid or its salts, or nitriles such as dialkyl esters, acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and metaallyl sulfonic acid Or salts thereof, alkyl vinyl ethers, N-acrylamide, methyltrimethylammonium chloride, dimethyl diallyl ammonium chloride, dimethyl allyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride polyoxyethylene, polyoxypropylene Polyoxyalkylene methacrylamide, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, etc. , Polyoxyethylene and the like can be mentioned ethylene-allyl amine, polyoxyethylene allylamine, polyoxypropylene ethynyl alkylene vinylamine, polyoxypropylene vinylamine Take the propylene. The polymerization reaction is carried out using a known radical polymerization catalyst such as azobisisobutylnitrile, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, and the reaction temperature is selected in the range of about 35 ° C to 80 ° C. In saponifying the obtained vinyl ester polymer, the polymer is dissolved in alcohol and carried out in the presence of an alkali catalyst.

Alcohol, methanol, ethanol, butanol, etc. are mentioned, The density | concentration of the copolymer in alcohol is selected in the range of 0.1-50 weight%. As the saponification catalyst, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be used.

The amount of the catalyst used may be 1-100 mmol equivalents. In some cases, it is also possible to saponify with an acid catalyst.

As polyvinyl alcohol resin used by this invention, it is preferable that saponification degree is 67-97 mol% and polymerization degree is 200-3000. If saponification degree is less than 67% mole, there is a problem of undissolved polysaccharides when dissolving polyvinyl alcohol, and if it exceeds 97 mole%, there is a problem of slow dissolution rate, and if polymerization degree is less than 200, mechanical strength is insufficient. If there is more than 3000, there is a problem that the water solubility is lowered, which is undesirable.

When explaining the surfactant among the additives, the polyoxyethylene-based compound used as the surfactant is sprayed with the polyvinyl alcohol composite aqueous solution 20 on the coke 10 as a drug for strengthening the coke 10, the inside of the coke 10 It penetrates into the hollow portion (h) generated in the gap of the outside is coated on the outside coke 10, the outside serves to reinforce the coke 10 by acting to bind the polyvinyl alcohol to each other. In the present invention, M-TDE 1020, a polyoxyethylene-based surfactant, was used.

M-TDE 1020 has excellent interfacial activity to help polyvinyl alcohol to penetrate the coke 10 more widely and deeply into the coke 10.

Next, when explaining the preservative among the additives, the polyvinyl alcohol aqueous solution decays even if left at room temperature 1-2 months. This does not mean that the polyvinyl alcohol rots, but the water rots. Therefore, preservatives should be added to use polyvinyl alcohol solution for long term storage. The present inventors have a shelf life of at least 5 years using betacide, an isocyazoline-based preservative.

Looking at the configuration of Betacide,

Chemical Name: 1) CMIT (5-chioro-2-methyl-4isothiazolin-3-one) 1.15% Min

2) MIT (2-methyl-4isothiazolin-3-one) 0.35% Min

3) Water 98.5% Max

Betacide is a mixture containing the three compounds in the same amounts.

Looking at the embodiment and the comparative example using the polyvinyl alcohol complex aqueous solution used as the additive is prepared and mixed as follows.

To the polyvinyl alcohol having a saponification degree of 87.5 mol% and the polymerization degree of 1,700, 0.05 part by weight of a surfactant polyoxyethylene compound, 95 parts by weight of water, and 0.001 part by weight of preservative betacide were added to 4.99 parts by weight of polyvinyl alcohol to 90 ° C while stirring. The temperature is raised and dissolved for about 1 hour.

By dissolving as described above to prepare a polyvinyl alcohol composite aqueous solution (20). After spreading the prescribed amount using 2Kg of coke (10) on which the polyvinyl alcohol complex aqueous solution (20) was laid on the floor using a spraying device, it was left at room temperature for 12 to 20 hours and then put into a strength (DI) simple measuring instrument for 1 hour. After the rotation (RPM: 86) pulverization, only the coke 10 having a diameter of 15 mm or more is picked out and the weight is measured. (The size of the coke 10 before the pulverization is 55 mm in average diameter.) Table 1 shows. In this case, the DI value is good and the preservative is contained, so it can be used for a long time. In addition, the polyvinyl alcohol complex aqueous solution (20) does not smell, there is no problem in practical application.

[Measurement of physical properties]

D.I. Value:

1) Lab. Device: D.I. (Drum Index) simple measuring instrument (Drum I.D 250mm, Drum Length 400mm, Spraying device.

2) Experimental method: After spraying the prescribed amount using polyvinyl alcohol complex aqueous solution (20) (by test condition) to 2Kg of coke (10) laid on the floor using a spraying device, it was allowed to stand at room temperature for 12 to 20 hours. It is put in a simple measuring machine and rotated for 1 hour (RPM: 86) after grinding, and weighs only the coke 10 having a diameter of 15 mm or more. (The size of the coke 10 before grinding is 55 mm in average diameter.)

* DI%-> Coke (10) is put in the DI simple measuring instrument after a certain time of rotation at a certain RPM, except the pulverized coke (10 coke (10) diameter / initial input amount X100)

The same procedure as in Example 1, but 87.5 mol% saponification degree, 5 parts by weight of PVA of polymerization degree 1700, 95 parts by weight of water was heated to 90 ° C while stirring to dissolve for about 1 hour. 2kg of polyvinyl alcohol solution laid on the floor was sprayed using a spreading device using a spraying device, and then allowed to stand at room temperature for 12 to 20 hours, and then put into a DI simple measuring instrument (RPM: 86). After grinding, only the coke 10 having a diameter of 15 mm or more is picked out and weighed (the size of the coke 10 before grinding is 55 mm in average diameter). The DI value was measured in the above, and the results are shown in Table 1 below. Here is an example using only polyvinyl alcohol aqueous solution, but DI value is not good.

{Comparative Example 1}

In the same manner as in Example 1, except for spraying anything other than water to the coke 10, it was measured by the above method, the results are shown in Table 1 below.

In the same manner as in Example 1, but was added to the polyvinyl alcohol of saponification degree 87.5 mol%, polymerization degree 1700 to 5 parts by weight of polyvinyl alcohol 0.25 parts by weight of an acrylic compound of strength-enhancing agent, 94.75 parts by weight of water while stirring at 90 ° C. The temperature is raised to about 1 hour to dissolve.

By dissolving as described above to prepare a polyvinyl alcohol composite aqueous solution (20). Spray the prescribed amount to 2 kg of coke (10) on which the polyvinyl alcohol complex aqueous solution 20 was laid on the floor, spray the prescribed amount, and leave it at room temperature for 12 to 20 hours, and then rotate it for 1 hour by putting it in a DI simple measuring instrument. RPM: 86) After grinding, only the coke 10 having a diameter of 15 mm or more is picked out and weighed (the size of the coke 10 before grinding is 55 mm in average diameter). The D.I. value was measured in the above, and the results are shown in Table 1 below. In this case, the D.I. value is the highest due to the strength enhancer, but the acrylic polymer used as the strength enhancer has a high smell and is considered to have a problem in practical application.

* Acrylic compound is-Product name: E-270-Chemical name: Acyl copolymer.

In the same manner as in Example 1, to the polyvinyl alcohol having a saponification degree of 87.5 mol% and a polymerization degree of 1,700, 0.025 parts by weight of a surfactant polyoxyethylene compound and 94.975 parts by weight of water were added to 5 parts by weight of polyvinyl alcohol while stirring. The temperature is raised to 90 ° C and dissolved for about 1 hour.

By dissolving as described above to prepare a polyvinyl alcohol composite aqueous solution (20). Spray the prescribed amount to 2 kg of coke (10) on which the polyvinyl alcohol complex aqueous solution 20 was laid on the floor, spray the prescribed amount, and leave it at room temperature for 12 to 20 hours, and then rotate it for 1 hour by putting it in a DI simple measuring instrument. RPM: 86) After grinding, only the coke 10 having a diameter of 15 mm or more is picked out and weighed (the size of the coke 10 before grinding is 55 mm in average diameter). The DI value was measured in the above, and the results are shown in Table 1 below. Although the DI value is good here, it is judged that the polyvinyl alcohol composite aqueous solution 20 is unsuitable for long-term storage.

In the same manner as in Example 1, 17.5 parts by weight of a polyoxyethylene compound of surfactant, 93.75 parts by weight of water, and preservative Betacide 0.25 with respect to 57.5 parts by weight of polyvinyl alcohol in polyvinyl alcohol having a saponification degree of 87.5 mol% and a degree of polymerization of 1,700. It is dissolved in about 1 hour by heating up to 90 ° C. while stirring by weight.

PVA resins, surfactants and strength enhancers used in Examples 1 to 4 and Comparative Example 1, summarized the amount of use of preservatives and the like are summarized in Table 1 below.

division Polyvinyl Alcohol Plasticizer
water Surfactants antiseptic Experiment result division Resin polymerization degree
(1700) Resin
(Mall 87.5%) M-TDE1020 Acyl
copolymer Betacide D.I. % Example 1 4.994 95 0.005 - 0.001 96.5 Example 2 5 95 - - - 91.6 Example 3 5 94.75 - 0.25 - 96.7 Example 4 5 94.975 0.025 - - 96.4 Example 5 5 93.75 One - 0.25 96.6 Comparative Example 1 - 100 - - - 78.5

According to an embodiment of the polyvinyl alcohol composite aqueous solution to prevent coke differentiation to which the technique of the present invention is applied as described above, water and poly are used as the surfactant polyoxyethylene compound M-TDE 1020 and the preservative polyoxyethylene compound Betacide. When the polyvinyl alcohol composite aqueous solution 20 prepared by mixing vinyl alcohol is used, the hollow portion produced in the coke 10 is maintained by appropriately maintaining the strength of the coke 10 in the blast furnace to achieve breathability and combustibility. h) polyvinyl alcohol complex aqueous solution 20 is impregnated to minimize the hollow portion (h) to minimize the differentiation that may occur during the movement of the coke (10), thereby increasing the quality of the coke (10) It is an invention with great effect, such as improving the yield of coke.

10: coke 20: complex aqueous solution
h: hollow part

Claims

In the polyvinyl alcohol complex aqueous solution using a polyvinyl alcohol (PVA) resin, a surfactant, and a preservative mixed with water,
The polyvinyl alcohol resin has an average saponification degree of 65 to 97 mol%, the average polymerization degree of 200 to 3000 4.994 to 5 parts by weight, the surfactant is a polyoxyethylene-based surfactant M-TDE1020 0.005 ~ 1 parts by weight In the preservative, polyvinyl alcohol complex aqueous solution for preventing coke differentiation, which is prepared by adding 0.001 to 0.2 parts by weight of betacide and 93.75 to 95 parts by weight of water as an isocyazoline-based preservative.

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