JPS6150991B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to improvements in dust generation inhibitors. Coal, coke, various ores, etc. handled in factories generate dust during the estimation, crushing process, and transportation, and since this dust is mainly fine particles on the micron scale, it is easily blown away by wind. They become airborne and become a major cause of air pollution. Conventionally, water, an aqueous surfactant solution, a polymer resin, waste oil, etc. have been used as a dust prevention agent for this type of dust. However, these dust prevention mechanisms are to stabilize the dust particles by lowering their interfacial tension and keeping the surface wet. However, with water and conventional aqueous surfactant solutions, the dust-proofing effect disappears when they dry, and the effect is not long-lasting.Also, with polymer resins and waste oil, there is selectivity to dust.
In addition to secondary water pollution and organic gas generation, there were other drawbacks such as the failure to form a film to cover the surface of the powder during low-temperature periods. The present invention was developed as a result of various studies to eliminate the drawbacks of conventionally known dust prevention agents. It not only forms a film but also aggregates powder to increase the apparent particle size, preventing dust from scattering, and has stable performance against changes in outside temperature. This is a new invention in which a bituminous material is acylated with a soybean oil fatty acid, and its gist is that a bituminous material is acylated by adding soybean oil fatty acid to a bituminous material and heating it to acylate it, and 1-n-octadecylamino-3- The emulsion was prepared by blending aminopropane or 1-n-oleylamino-3-aminopropane with a solution of acetic acid or hydrochloric acid aqueous solution. To explain the present invention in more detail below, the bituminous material, which is one of the components of the dust generation prevention agent of the present invention, is obtained by adding soybean oil fatty acid to the bituminous material and heating it to acylate it. It can be obtained by heating at a temperature of 150 to 250°C for 3 to 5 hours at normal pressure with the addition of a catalyst if necessary.For example, it can be used for straight asphalt obtained from petroleum, blown asphalt, deasphalt, and dry distillation of coal. Coal tar pitch etc. obtained by this process, and one or two types of aromatic oils produced as by-products during the extraction of lubricating oil during the petroleum refining process.
The seeds or more are acylated with soybean oil fatty acids, and ether groups, ester groups,
This type has a carboxy group or carbonyl group introduced. Such acylated bitumen can be obtained as described above, and the reaction proceeds rapidly if sodium perchlorate is used as a catalyst as described above. Therefore, it can be confirmed by the infrared absorption spectrum that the bituminous material has been acylated. That is, the formation of carboxylic acid and carboxylic acid salts was confirmed by infrared absorption spectrum, and 1725-1700 cm ^-1 and 1320
This can be confirmed by the absorption spectrum becoming stronger in the range of ~1211 cm ^-1 . In addition, 1 which is another component of the dust generation preventive agent of the present invention
A solution prepared by dissolving -n-octadecylamino-3-aminopropane or 1-n-oleylamino-3-aminopropane in acetic acid or an aqueous chlorine solution assists in forming an aqueous emulsion of the acylated bitumen. An aqueous solution containing about 3 to 10% by weight of a diamine salt obtained by adding 1-n-octadecylamino-3-aminopropane or 1-n-oleylamino-3-aminopropane to an aqueous hydrochloric acid solution and stirring with heating. It is. The dust generation inhibitor of the present invention contains 20 to 60% by weight of the bituminous material acylated with the soybean oil fatty acid and 1-n-octadecylamino-3-aminopropane or 1-n-
80-40% by weight of an acidic aqueous solution of oleylamino-3-aminopropane dissolved in acetic acid or hydrochloric acid aqueous solution
and by stirring vigorously in a commonly known emulsifying device such as a homogenizer or a colloid mill. In this case, if a deliquescent substance such as calcium chloride or magnesium chloride is present as an emulsion stabilizer, the stable storage period of the emulsion will be approximately 3 months, and the stable storage period when this is not used will be approximately 3 months. It can be doubled. When using the emulsion-like dust generation preventive agent of the present invention, it is diluted as it is or, if necessary, diluted to the desired concentration, and if necessary, other known auxiliary agents are added. It is sprayed and penetrated into powdery materials, such as crushed coal and ore, that are on the way to the transfer equipment.
As mentioned above, the dust generation preventive agent of the present invention is an emulsion, so it is easy to handle, and the bituminous material contained therein is in an acylated form, which is an emulsification aid.
It floats stably in a colloidal form in n-octadecylamino-3-aminopropane or 1-n-oleylamino-3-aminopropane salt aqueous solution, and its thermal sensitivity is dulled by acylation of bitumen. As a result, it can be used in almost the same condition in both summer and winter, and due to the adhesiveness of the acylated bitumen that penetrates into the gaps between particles, it can be used to reduce fine particles to a diameter of several mm. Since it is made into aggregates, it has the effect of preventing the generation of dust from added particulates such as pulverized coal and iron ore. Next, the film forming performance of the dust generation preventive agent of the present invention is shown in the table.

【table】

[Table] In the above table, the products of the present invention are those according to Example 3,
In addition, PK-4 asphalt emulsion based on JIS-K-2208 is made from PK-4 asphalt emulsion made from JIS-K-2207 as a raw material, and polyoxyethylene lauryl ether is made from 4 moles of ethylene oxide. Addition-polymerized polyoxyethylene lauryl ether with a molecular weight of 300 to 350 was used. Also, the "thickness at which the inhibitor penetrates into the gaps in the fine powder" is
Iron ore (Kriboilok) fine powder with an amount of 80 to 95% by weight passing through a 0.074 mm sieve is made into a conical shape with a normal angle of 30 degrees.
An inhibitor is sprayed from the top of the slope at a concentration of 3% by weight at a rate of 2/ ^m2 , and the film thickness is measured. Thick films are judged as "good" and thin films are judged as "bad". The water was considered to be of inferior quality and was rated as "none". (Since it was sprayed on a conical slope at a normal angle of 30 degrees, the material that did not penetrate flowed to the foot of the mountain.) In addition, "stickiness after drying of the film" was determined by spraying the preventive agent using the method described above.After one day, the film was heated to 25℃. Stickiness was examined by touching, and those that were sticky to the fingers were rated as "poor", those that were not sticky were rated as "good", and those that did not form a film were rated as "none". In addition, "adhesiveness at high temperatures" is determined by the same method as above at 45℃ from the time of spraying until the inhibitor forms a dry-to-the-touch film.
The evaluation was made under the condition that it was maintained at In addition, "tackiness at low temperature" was measured at 5℃ using the same method as above.
The evaluation was made under the condition that it was maintained at Next, the crushing strength of the dust generation preventive agent of the present invention is shown in the table.

[Table] The amounts added in the above table are expressed in weight% based on the weight of powdered coal. Moreover, the product obtained in Example 3 was used as the product of the present invention.
Also, JIS-K-2208PX-4 asphalt emulsion
PK-4, an emulsion made from JIS-K-2207
Asphalt emulsion was used. As the nonionic surfactant, polyoxyethylene lauryl ether having a molecular weight of 300 to 350 was used which was polymerized with 4 moles of ethylene oxide. The crushing strength was measured by adding each inhibitor to fine particles with a particle size of 0.4 mm or less and the number of sieve vibrations until the aggregated fine powder was crushed again to a particle size of 0.4 mm or less. The sieve was vibrated horizontally in a circular motion of 5 cm radius 80 times/hour and vertically in a vertical direction of 1 cm at a rate of 60 times/hour. Next, the present invention will be further explained by giving examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof. Example 1 95 parts by weight of aromatic oil heated to 110°C was added to 70°C.
Add and mix 5 parts by weight of soybean oil fatty acid heated to
The product of the present invention was stirred for 4 hours at 160°C and heated for 3 hours after the intense foaming subsided.
A composition of acylated bituminous material (hereinafter referred to as base agent A) was obtained. Separately, 1 part by weight of acetic acid and 1-n-octadecylamino-
Add 2 parts by weight of 3-aminopropane and mix and stir.
A diamine salt aqueous solution (hereinafter referred to as base agent B), which is one of the components of the product of the present invention, was obtained. Next, 40 parts by weight of the base agent (A) and 60 parts by weight of the base agent (B) were thoroughly mixed and stirred using a homogenizer to obtain an emulsion-like dust generation preventive agent of the present invention. Example 2 5 parts by weight of soybean oil fatty acid heated to 70°C was added and mixed to 95 parts by weight of straight asphalt heated to 160°C, and the mixture was stirred while being maintained at 210°C for 2 hours to prevent severe foaming. The mixture was cooled and aged for 4 hours to obtain an acylated bituminous material (hereinafter referred to as base agent A), which is one of the compositions of the products of the present invention. Separately, 1 part by weight of hydrochloric acid and 2 parts by weight of 1-n-oleylamino-3-aminopropane were added to 97 parts by weight of water heated to 50°C and mixed and stirred to obtain one composition of the present invention. A diamine salt aqueous solution (hereinafter referred to as base agent B) was obtained. Next, 40 parts by weight of the base agent (A) and 60 parts by weight of the base agent (B) were thoroughly mixed and stirred using a homogenizer to obtain an emulsion-like dust generation preventive agent of the present invention. Example 3 35 parts by weight of aromatic oil heated to 145°C are mixed and stirred with 60 parts by weight of straight asphalt heated to 170°C, and 5 parts by weight of soybean oil fatty acid heated to 70°C are added and mixed, The mixture was stirred while maintaining the temperature at 180°C for 3 hours, and after the intense foaming subsided, it was aged for 4 hours to obtain an acylated bituminous material (hereinafter referred to as base agent A), which is one of the compositions of the product of the present invention. . Separately, 1 part by weight of acetic acid and 1-n-octadecylamino-
2 parts by weight of 3-aminopropane and magnesium chloride
0.5 part by weight was added in the above order and mixed and stirred to obtain a diamine salt aqueous solution (hereinafter referred to as base agent B) which is one of the components of the product of the present invention. Next, 40 parts by weight of the base agent (A) and 60 parts by weight of the base agent (B) were thoroughly mixed and stirred using a homogenizer to obtain an emulsion-like dust generation preventive agent of the present invention. In addition, in Example 1, based on the total weight of the blend of aromatic oil and soybean oil fatty acid, in Example 2, based on the total weight of the blend of straight asphalt and soybean oil fatty acid, and in Example 3, the aromatic The acylation reaction time could be shortened by adding 0.1% by weight of sodium perchlorate to the total weight of the oil, straight asphalt, and soybean oil fatty acid formulation. In addition, the reason why magnesium chloride was added in Example 3 was to impart storage stability, and in Examples 1 and 2, the addition of magnesium chloride or calcium chloride did not improve storage stability. This is about three times as long as in the case of the case. Next, the product of the present invention obtained in Example 3 was added to oil coke and iron ore (krivoilok),
The results of measuring changes in particle size distribution are shown in the table.

【table】

[Table] However, the test conditions in the table above are as follows.
The samples were 500 g each of oil coke and iron ore (Kriboilok), and the composition of the product of the present invention was 30 parts by weight of the base agent (A) obtained in Example 3 and 70 parts by weight of the base agent (B) obtained in Example 3. 50 parts by weight of the product of the present invention mixed with 30 parts by weight of water
Parts by weight are added. The addition rate of the present invention product was 0%, 2%, 4%, and 6% by weight of the present invention product prepared as described above. The product of the present invention was added to the sample under the above conditions, and after air drying for 3 days, the particle size distribution was measured using a sieve. From the results shown in the table, it can be seen that in both samples, as the addition rate of the product of the present invention increases, the average particle size increases. In particular, in the case of oil coke, if 2% by weight or more of the present invention is added, the weight% of the particle size that passes through a 0.3 mm sieve will be very small, 0.1% or less, so it is the main cause of dust generation. It can be seen that these fine particles are aggregated and are difficult to scatter, indicating that they have the effect of suppressing dust generation. Also, even in the case of fine-grained iron ore, 0.3mm
When no additives were added, the weight percent of particles passing through a 0.3 mm sieve was 53.4 percent by weight, but when 6 percent by weight of the present invention was added, the weight percent of particles passing through a 0.3 mm sieve was 4.5 percent.
It can be seen that it is effective not only in carbonaceous agents such as oil coke but also in iron ore. Next, the comparison results of the aggregate effect between the product of the present invention and a typical commercially available inhibitor are shown in a table.

[Table] The products of the present invention in the above table were prepared as described in Example 3, and the other inhibitors were prepared by adding 30 parts by weight of water to 50 parts by weight of a stock solution of a commercially available inhibitor. used. The test conditions for the results shown in the table above are as follows. The sample was 500 g of coal containing 13% by weight of particles with a particle size of 2.5 mm or more.The additive rate of inhibitor was 0%, 0.8%, and 1.5% by weight.
%, 2.5%, 5%, 7.5%, 9.5%, 10%. At the time of particle size measurement, after adding each inhibitor, the percentage of particle size that remained on a 2.5 mm sieve was compared in weight % of samples that were air-dried for 3 days. Three types of use inhibitors were used: the product of the present invention, a polyethylene glycol nonionic surfactant solution, and a vinyl acetate nonionic surfactant solution. Further, the amount of the inhibitor added was expressed as an addition weight % based on the weight of powdered coal. In addition, polyethylene glycol with a molecular weight of 600 was used as the polyethylene glycol nonionic surfactant solution. The vinyl acetate nonionic surfactant is polyoxyethylene lauryl with a molecular weight of 300 to 350, which is obtained by adding and polymerizing 4 moles of ethylene oxide to a commercially available vinyl acetate emulsion for preventing dust generation.
A mixture containing 0.2% by weight of ether was used. Under the above conditions, the product of the present invention and each commercially available inhibitor were added to the sample, and a table of results was obtained by measuring the proportion of particles with a particle size of 2.5 mm or more. From the results shown in the table above, it can be seen that the product of the present invention is superior in agglomeration effect and dust effect as compared to commercially available inhibitors. In this specification, aromatic oil refers to "Nelson.WL, Petroleum Retining Engineering
4th Ed" (1958) as a classification of aromatic oils based on UOP characteristic coefficients, and "Lane.EC et af, US
Buveau of Mines Report of Investigation3279
(1935) as a classification of aromatic oils based on API specific gravity, and refers to those with a UOP characteristic coefficient of 11.4 or less, an API specific gravity of 20 or more, a viscosity index of 24, or less, and an aniline point of 20°C or less.

Claims (1)

[Claims] 1. A bituminous material obtained by adding soybean oil fatty acid to a bituminous material and acylating it by heating, and 1-n-octadecylamino-
A dust generation preventive agent characterized in that an emulsion is prepared by blending 3-aminopropane or 1-n-oleylamino-3-aminopropane with a solution of acetic acid or an aqueous chlorine solution. 2. The dust generation prevention agent described in claim 1, characterized in that the bituminous material is straight asphalt or aromatic oil, or a mixture of straight asphalt and aromatic oil. agent.