JPH0231018B2 - - Google Patents

Description

[Detailed description of the invention]

(a) Object of the invention (industrial application field) The present invention relates to a treatment agent for promoting dehydration of granulated slag. (Prior art) The iron and steel manufacturing industry produces a large amount of slag as a by-product. In particular, granulated slag obtained by rapidly cooling and granulating molten slag taken out from a blast furnace with water has latent hydraulic properties and is important as a raw material for cement. In order to use granulated slag as a raw material for cement, it is necessary to dry and crush the granulated slag. The water content of granulated slag is 4%.
If the water content is below 4%, the slag will dry due to the heat generated during pulverization, so if the water content of the granulated slag can be reduced to 4% or less, there is no need for further drying. Regarding the method of drying granulated slag, it is possible to spread wet granulated slag thinly on the ground and dry it in the sun, but the required ground area is too large to dry a huge amount of slag. Not practical.
Therefore, most of the granulated slag is piled up in the open while still wet and left to dry naturally in the form of thick piles, and is shipped with a moisture content of about 10 to 8% to cement manufacturers. The reality is that these materials are further heated and dried. (Problems to be Solved by the Invention) Regarding this point, a drying method has recently been proposed that utilizes heat sources that were wasted in steel mills.
However, since granulated slag has a high affinity with water, it requires a large amount of heat, and the amount of slag that must be dried is enormous, so this method requires huge drying equipment and the equipment cost is extremely high. It has the disadvantage of becoming The present invention was made as a result of research to improve this situation by treating granulated slag with an appropriate chemical. Japanese Patent Publication No. 52-43477 states that ``(A) an ionic surfactant having a polyoxyalkylene chain in its molecule and having a cloud point of 35°C or less; and (B) a primarily hydrophobic oxyalkylene group (i.e. , an anionic surfactant having a hydrophobic polyoxyalkylene chain in the molecule (oxyalkylene groups other than -CH ₂ CH ₂ O-) and a dehydrating agent for wet fine ores.
An invention has been disclosed. The publication further states that sodium alkylbenzenesulfonate and sodium dioctyl sulfosuccinate are used for dehydration of pulverized coal, draining of silica sand, etc.
There is a statement that anionic surfactants such as salts are said to be effective. However, there is no description suggesting that this dehydrating agent can be used for dehydrating granulated slag, which is not an ore but an inorganic solid that is artificially produced and has latent hydraulic properties. JP-A No. 57-84708 describes the general formula RO− (AO
) - _o SO ₃ M (wherein R is an alkyl group or alkenyl group having 8 to 24 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 100). A filtration and dewatering performance improver for a water-insoluble or slightly water-soluble metal hydroxide aqueous slurry is disclosed. However, this publication does not mention or suggest what kind of effects can be obtained when this filtration and dehydration improver is applied to other minerals, such as complexes of multiple metal oxides. . Generally, granulated slag has CaO and SiO ₂ as its main components.
Furthermore, it contains Al ₂ O ₃ , MgO, etc. These oxides do not exist in a free state themselves in the slag, but are bonded to each other, such as CaO and
Calcium silicate compounds are made with SiO ₂ .
Therefore, even if slag comes into contact with water, it will react with the water,
It does not change into a mixture whose main component is Ca(OH) ₂ . U.S. Pat. No. 4,210,531 discloses that after an aqueous slurry of concentrate is treated with a polyacrylamide flocculant, a composition containing an anionic surfactant (e.g. dialkyl sulfosuccinate) is added and mixed into the slurry. , a method for subsequently removing water from the slurry is disclosed. However, there is no description in this specification that suggests that this composition can be used for dewatering granulated slag, which is an inorganic solid that is artificially produced and has latent hydraulic properties. U.S. Pat. No. 4,447,344 discloses compositions containing certain nonionic surfactants and hydrotropic agents for adding to an aqueous slurry of particulate minerals to promote dehydration of the particulate minerals. Disclosed is an invention of a product and a method for dehydrating particulate minerals using the same. This specification discloses compounds in which a sulfonate group is bonded to a monovalent hydrocarbon group having 8 to 9 carbon atoms as a hydrotropic agent, but these compounds are too hydrophilic and cannot be used as surfactants. This is a compound that does not fall into the category of . In addition, this specification also describes this composition as
There is no description suggesting that it can be used for dewatering granulated slag, which is an inorganic solid that is artificially produced and has latent hydraulic properties. The dehydrating agents disclosed in Japanese Patent Publication No. 52-43477, Japanese Patent Application Laid-open No. 57-84708, and U.S. Pat. problems caused by bubbles. Even if the generated foam can be extinguished using an antifoaming agent, these dehydrating agents will generate foam again in the next step, and it will be necessary to extinguish the foam again using an antifoaming agent. If the antifoaming agent is used in this manner, the amount of antifoaming agent required as a whole becomes too large, which is undesirable. Further, even if an antifoaming agent is added to a dehydrating agent containing an anionic surfactant, it is difficult to suppress foaming. The inventors of the present invention have discovered that a cationic surfactant accelerates the drying of water-wet granular slag, and have developed a method for treating water-wet granular slag with a cationic surfactant and then drying it, and a method for drying the water-wet granular slag. We have previously proposed a drying aid for granular slag containing a surfactant as an active ingredient (see Japanese Patent Application Laid-open No. 16841/1983). However, this drying aid also has remarkable foaming properties. If an antifoaming agent is mixed with this drying aid, foaming can be suppressed for a few days after blending, but after that, foaming will gradually begin.
If a drying aid is used that has been mixed with an antifoaming agent for some time, or the drying aid mixed with an antifoaming agent is recycled and reused, the drying aid may remain in the slag processing equipment for a long time. It has been found that there is a problem in that there is a tendency for foaming. By the way, what is completely surprising is that when a certain anionic surfactant and a certain cationic surfactant are used in combination, the dehydration of water-wet granulated slag is accelerated and also for a long period of time. It has been found that foaming can be suppressed. Therefore, the present invention contains a specific anionic surfactant and a specific cationic surfactant,
An object of the present invention is to provide a composition that promotes dehydration of water-wet granulated slag and exhibits suppressed foaming properties. (b) Structure of the invention (means for solving problems) The present invention consists of (a) the following formula RO−(CH ₂ CH ₂ O)− _o SO ₃ M … (Formula 1) or RCOOCH ₂ O−(CH ₂ CH ₂ O)− _o SO ₃ M…(Formula 3) (However, in the above formula, R has 11 carbon atoms.
~30 monovalent hydrocarbon group, R' is an H atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms. M is H ⁺ ,
Na ⁺ , K ⁺ , NH ₄ ⁺ , 1/2Mg ²⁺ , 1/2Ca ²⁺ or monovalent organic cations having 10 or less carbon atoms. The average value of n is 3-20. ) one or more selected from the group consisting of anionic surfactants represented by any of the following: (b) at least one carbon atom in the molecule of 11 to
one or more selected from the group consisting of cationic surfactants having 30 monovalent hydrocarbon groups, and 79 to 23% by weight of the above anionic surfactant, based on the total of both The gist of this invention is a treatment agent for promoting dehydration of granulated slag, which is characterized by containing a cationic surfactant in a proportion of 21 to 77% by weight. The anionic surfactant used in the present invention is selected from compounds represented by formulas 1 to 3 below. [Formula 1 _] RO-( _CH2CH2O ) _-oSO3M ( _e.g. polyoxyethylene alkyl ether sulfate salt, polyoxyethylene alkyl phenyl ether sulfate salt) (For example, sulfate ester salt of amide of fatty acid and H(OCH ₂ CH ₂ )NH ₂ ) [Formula 3] RCOOCH ₂ O−(CH ₂ CH ₂ O)− _o SO ₃ M (For example, fatty acid, formaldehyde, and triethylene glycol (However, in the above formulas 1 to 3, R is the number of carbon atoms
A monovalent hydrocarbon group having 11 to 30 carbon atoms; R' is an H atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms; M is H ⁺ ,
Na ⁺ , K ⁺ , NH ₄ ⁺ , 1/2Mg ²⁺ , 1/2Ca ²⁺ or monovalent organic cations having 10 or less carbon atoms. n is the average number of moles of ethylene oxide added per mole of surfactant, from 3 to 20. ) Specific examples of anionic surfactants represented by these formulas are as follows: [Formula 1] RO-(CH ₂ CH ₂ O)- _o SO ₃ M: C ₁₂ H ₂₅ O(CH ₂ CH ₂ O) ₃ SO ₃ Na, C ₁₆ H ₂₃ O (CH ₂ CH ₂ O) ₆ SO ₃ Na C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₄ SO ₃ Na C ₁₇ H ₃₅ CONH (CH ₂ CH ₂ O) ₈ SO ₃ Na [Formula 3] RCOOCH ₂ O− (CH ₂ CH ₂ O) − _o SO ₃ M: C ₁₁ H ₂₃ COOCH ₂ O(CH ₂ CH ₂ O) ₃ −SO ₃ Na and the like. In formulas 1 to 3 above, n is preferably 3 to 10. The cationic surfactant used in the present invention is
As described in JP-A-60-16841 cited above, it is a cationic surfactant having a monovalent hydrocarbon group having 11 to 30 carbon atoms in its molecule. In particular, free bases and acid addition salts thereof represented by the general formula R-X...(Formula 4), and quaternary nitrogen-containing cations represented by the general formula [R-X] ⁺ G ^-... (Formula 5) surfactant [However, in formulas 4 and 5, R has 11 carbon atoms
~30 monovalent hydrocarbon groups. X is

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[Formula] A, A', A'' and A are H atoms and have 1 to 7 carbon atoms
A monovalent hydrocarbon group or a hydroxyalkyl group having 1 to 4 carbon atoms. A, A', A'', and A may or may not all be the same. Q, Q', Q'', and Q are monovalent hydrocarbon groups having 1 to 7 carbon atoms, or monovalent hydrocarbon groups having 1 to 7 carbon atoms; 4 hydroxyalkyl group. Q, Q', Q'' and Q may or may not all be the same. R' is a monovalent hydrocarbon group having 1 to 30 carbon atoms, and may be the same as or different from R. Z and Z' are divalent hydrocarbon groups having 1 to 7 carbon atoms, and may be the same or different. G is a monovalent anion. The represented compounds are explained in more detail below.

[Formula] R is exemplified by an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, etc., and A and A' are exemplified by an H atom. Representative examples include aliphatic primary amines such as stearylamine and oleylamine.

[Formula] R is exemplified by an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, etc., and Z is -C ₂ H ₄
-, -C ₃ H ₆ -, etc. are exemplified, and A and A' are exemplified by H atoms, -C ₂ H ₄ OH, etc. for example

[Formula] (where R is a residue such that RCOOH is naphthenic acid or fatty acid).

[Formula] Examples of R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, and an aralkyl group. An example is stearamidine.

[Formula] R is exemplified by an aliphatic hydrocarbon group. A typical example is alkylguanidine.

[Formula] R is exemplified by an aliphatic hydrocarbon group. Examples of A include -CH ₃ and -C ₂ H ₅ .

[Formula] Examples of R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, and an alkylphenyl group. Examples of A include _-CH3 , _-C2H5 , _-C2H4OH and _the like _. Typically, R is a residue such that RCOOH is naphthenic acid or a fatty acid, and A is -C ₂ H ₄ OH (e.g. 1-hydroxyethyl-2-heptadecenyl-2- imidazoline). Further, the compound represented by Formula 5 will be explained in more detail below.

[Formula] R is exemplified by an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, an alkyl phenyl group, etc., and Q, Q' and Q'' are -CH ₃ , -C ₂ H ₅ ,−
Examples include _C6H5 , _-CH2 - _C6H5 , _{-C2H4OH , and} the _like . Examples include stearyl trimethyl ammonium halide, cetyl triethyl ammonium halide, lauryl dimethyl benzyl ammonium halide, and the like.

[Formula] R and R' are exemplified by aliphatic hydrocarbon groups, alicyclic hydrocarbon groups substituted with alkyl groups, aralkyl groups, alkylphenyl groups, etc., and Q and Q' are -CH ₃ , -C ₂ H ₅ ,−
Examples include _C6H5 , _-CH2 - _C6H5 , _{-C2H4OH , and} the _like . Examples include dilauryl dimethyl ammonium halide.

[Formula] R is exemplified by an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, an alkyl phenyl group, etc., and Z is exemplified by -CH ₂ -. Q,
Q′ and Q″ are −CH ₃ , −C ₂ H ₅ , −C ₆ H ₅ , −CH ₂ −
Examples include C ₆ H ₅ and -C ₂ H ₄ OH.

[Formula] R is exemplified by an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, an alkylphenyl group, etc., and Z is exemplified by -C ₆ H ₄ -. Q,
Examples of Q' and Q'_' include _-CH3 , _-C2H5 , _-C2H4OH , and the like _.

[Formula] R is exemplified by an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, an alkyl phenyl group, etc., and Z is -CH ₂ -, -C ₂ H ₄ -, etc. is exemplified. Q, Q′ and Q″ are −CH ₃ , −C ₂ H ₅ , −
Examples include C ₂ H ₄ OH.

[Formula] Examples of R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, and an alkylphenyl group. Examples of Z include -C ₂ H ₄ -, -C ₃ H ₆ -, and the like. Q, Q′ and Q″ are −CH ₃ , −C ₂ H ₅ ,
_-C2H4OH etc. _are illustrated.

[Formula] Examples of R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, and an alkylphenyl group. Q is −CH ₃ , −C ₂ H ₅ , −
Examples include C ₂ H ₄ OH.

[Formula] Examples of R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, and an alkylphenyl group. Q is −CH ₃ , −C ₂ H ₅ , −
Examples include C ₂ H ₄ OH.

[Formula] Examples of R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, and an alkylphenyl group. Q is −CH ₃ , −C ₂ H ₅ , −
Examples include C ₂ H ₄ OH.

[Formula] Examples of R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, and an alkylphenyl group.

[Formula] Examples of R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, and an alkylphenyl group. Z is exemplified by _-CH2- .

[Formula] Examples of R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, and an alkylphenyl group. Z is −C ₆ H ₄ −, −C ₆ H ₄ −CH ₂
- etc. are exemplified.

[Formula] Examples of R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, and an alkylphenyl group. Z is exemplified by _-CH2- .

[Formula] Examples of R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, and an alkylphenyl group. Z is exemplified by _-CH2- .

[Formula] Examples of R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, and an alkylphenyl group. Q and Q' are −CH ₃ , −C ₂ H ₅ , −
Examples include C ₂ H ₄ OH.

[Formula] Examples of R and R' include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group substituted with an alkyl group, an aralkyl group, and an alkylphenyl group. Q is −CH ₃ , −
Examples include C ₂ H ₅ , -C ₂ H ₄ OH, etc., and Z is -CH ₂ -
is exemplified. 〓〓

[expression] or

[Formula] It is a quaternized product of 2-substituted benzimidazole. It is not yet clear which of the two nitrogen atoms in the imidazole ring should be quaternized, and there are two ways of thinking about it. Examples of R include an alkyl group.
Examples of Q and Q _' include _-CH3 , _-C2H5 , _-C2H4OH and the like _.

[Formula] R is exemplified by an alkyl group. Q and Q' are −CH ₃ , −C ₂ H ₅ , −
Examples include C ₂ H ₄ OH. 〓〓

[Formula] R is exemplified by an alkyl group. Examples of Z include _-CH2- , _{-C2H4- ,} and the like. Q, Q′, Q″ and Q are −CH ₃ ,
_-C2H5 , _{-CH2 - C6H5 , etc.} are exemplified. The dehydration promoting treatment agent of the present invention contains the anionic surfactant and the cationic surfactant, the former being 79 to 23% by weight and the latter being 21 to 23% by weight based on the total weight of both.
Contains 77% by weight. If the former is more than 79% by weight, the foaming properties of the dehydration-promoting treatment agent will increase and approach the foaming properties of the anionic surfactant alone, making it difficult to suppress foaming, which is not preferable. If the latter amount exceeds 77% by weight, the foaming properties of the dehydration accelerating treatment agent will increase and approach the foaming properties of the cationic surfactant alone, making it difficult to suppress foaming, which is not preferable. In particular, for the total weight of both,
When the ratio is 79 to 50% by weight and the latter is 21 to 50% by weight, the foaming power of the dehydration promoting treatment agent is suppressed, and foaming can be easily prevented by using an antifoaming agent in combination, and the dehydration promoting effect is also excellent. Furthermore, it is preferable because the slag treated with this treatment agent will not have a substantial adverse effect on the hardening speed of cement or the strength of the cured product, which is made using the slag as a raw material. The dehydration promoting treatment agent of the present invention may include, if necessary,
It goes without saying that other components (for example, antifoaming agents, viscosity modifiers, fungicides, solvents, etc.) that do not have an adverse effect on the slag or the surfactant may be included. As the antifoaming agent, it is preferable to use a silicone antifoaming agent, and the blending ratio thereof is 0 to 10% of the silicone antifoaming agent based on the total weight of the anionic surfactant and the cationic surfactant.
It may be 100% by weight, particularly preferably 5 to 50% by weight. If the ratio of the dehydration-promoting treatment agent of the present invention to the granulated slag is too small, the dehydration-promoting effect will be weak, and if it is used in too large a quantity, the treatment agent will only be wasted and the dehydration-promoting effect will reach a plateau. The total amount of the anionic surfactant and the cationic surfactant is 1 to 0.002% by weight, particularly preferably, based on the dry weight of the granulated slag to be treated.
The content is preferably 0.5 to 0.005% by weight. The granulated slag to be treated using the treatment agent of the present invention may be immersed in water or taken out of water as long as it is wet with water. When treating granulated slag using the treatment agent of the present invention, this treatment agent is used in the form of a solution. It is particularly preferable to use it as an aqueous solution. When the granulated slag is immersed in water, it can be treated by adding the treatment agent as it is or as a solution into the immersed water and stirring. Also, when granulated slag is taken out of water,
A method of immersing the granulated slag in a solution of the treatment agent or a method of spraying the solution of the treatment agent onto the granulated slag that has been taken out of water can also be adopted. In addition, there is a method in which the treatment agent is added as it is or as a solution to circulating water for producing granulated slag, which is used to produce granulated slag by injecting water into molten slag. If the surfactant concentration (i.e., the total concentration of the anionic surfactant and the cationic surfactant) in the solution used for dehydration acceleration treatment of granulated slag is too dilute, the dehydration acceleration effect will decrease. Therefore, the content is preferably 0.003% by weight or more, particularly 0.005% by weight or more. On the other hand, if the concentration of the surfactant is too high, the proportion of the surfactant used in the granulated slag will be too large and will be wasted, so it is usually best to keep this concentration below 2% by weight. preferable. When the dehydration-promoting treatment agent of the present invention is used as an aqueous solution for dehydration-promoting treatment of granulated slag, depending on the quality of the water used as a solvent, the cationic surfactant contained in the treatment agent may cause precipitation. There is. In such cases, a cationic surfactant in the treatment agent should be selected that does not cause precipitation in the water. It can be determined whether a cationic surfactant is suitable for use in water by dropping the cationic surfactant into the water and checking whether precipitation occurs. For example, when the SO ₄ ^2- ion content in water is high, the cationic surfactant
Quite a lot of things precipitate. When the treatment agent of this invention is used to promote dehydration of granulated slag, the removal of water becomes extremely rapid, and
Even by draining (that is, dripping off adhering water) for about 1 minute to 1 hour, the moisture content of the slag is significantly lower than that of slag that has not been subjected to this treatment. However, the granulated slag that has been subjected to dehydration acceleration treatment using the treatment agent of the present invention may be dried,
If necessary, draining may be performed before drying.
Natural drying is usually sufficient. Natural drying here means drying without artificial heating. Therefore, the latent heat required for the evaporation of water is supplied from the heat possessed by the slag itself, heat conduction from the atmosphere, the ground used for drying, etc., and radiant heat from the sun. However, even when subjected to forced drying, the effects of the present invention are fully exhibited, so the present invention is not particularly limited by the drying method. The dehydration promoting treatment agent of the present invention also has the effect of preventing caking of granulated slag. In this specification, the term "water content" refers to the ratio of water weight to wet weight. (Example) Hereinafter, the present invention will be explained in detail with reference to Examples. Example 1 As a cationic surfactant

Using acetate of [formula], C ₁₂ H ₂₅ O as anionic surfactant
_{( CH2CH2O} ) _{3SO3Na was} used. Both were mixed at the weight ratio shown in Table 1, and the mixture was dissolved in tap water to prepare a solution with a concentration of 250 ppm (by weight). The foaming of this solution immediately after dropping was measured at a temperature of 40°C using the Ross-Miles method. For comparison, a solution containing only the cationic surfactant or only the anionic surfactant at a concentration of 250 ppm (by weight) was also measured for foaming immediately after the solution was dropped. Table 1 shows the foam height results. It can be seen that the composition of the present invention has significantly reduced foaming.

[Table] For each experiment, wet granulated slag was collected to a dry weight of 500 g, and after immersing and stirring in 500 g of a surfactant solution of one of the above experiment numbers ~ at 40℃ for 2 minutes. The mixture was heaped up in a conical shape in a stainless steel wire colander (weight known) and left to air dry at room temperature. The pH of the treatment solution after treating the slag was in the range of 9.0 to 9.2. For comparison, tap water without added surfactant
Add 500g of granulated slag (converted to dry weight) to 500g.
After being immersed and stirred at 40°C for 2 minutes, the mixture was similarly raised in a conical shape in a colander and allowed to air dry at room temperature at the same time (experiment number). The room temperature during air drying was kept within the range of 25-15°C. The moisture content of the slag 1 hour and 48 hours after the start of standing was determined by measuring the total weight of the colander and slag.
Calculated using the following formula. Moisture content (%) = [1-500 (g) / measured weight (g) -
Weight of colander (g)]×100 The results obtained are shown in Table 2.

[Table] From the results in Tables 1 and 2, treating granulated slag with an anionic surfactant and/or a cationic surfactant can promote dehydration. It can be seen that the foaming properties of the surfactant also decrease during dehydration acceleration treatment. Example 2 The blending ratio of anionic surfactant and cationic surfactant was 65:35 (weight ratio), and the total of both was
A composition containing 25 parts by weight of a silicone antifoaming agent (using Dow Corning product FSX-001) per 100 parts by weight was dissolved in industrial tap water to determine the concentration.
A 125 ppm (by weight) solution was prepared. The anionic surfactant used here is C ₁₈ H ₃₇ CONH (CH ₂ CH ₂ O) _o SO ₃ Na (average value of n is 6), and the cationic surfactant is A to L below.
Either.

【table】

[Table] When the foaming of the above solutions was measured at 25°C using the Ross-Miles method, the foam height immediately after dropping was zero for all solutions. After immersing and stirring 601 g of wet granulated slag (moisture content 16.8%) (500 g in dry weight) at 25°C for 2 minutes in 500 g of any of the above solutions,
It was air-dried in the same manner as in Example 1. The pH of the solution after treating the slag was within the range of 9.0 to 9.2. For comparison, 601 g of the above wet granulated slag was added to 500 g of industrial tap water without adding surfactant.
After being immersed and stirred at ℃ for 2 minutes, it was simultaneously air-dried at room temperature in the same manner. The pH of the tap water after treating the slag was 9.1 (experiment number). The moisture content of the slag 1 hour and 52 hours after the start of air drying was measured in the same manner as in Example 1. The results obtained are shown in Table 3.

[Table] From the above results, it can be seen that according to the present invention, dehydration and drying of slag can be significantly accelerated, and foaming of the treatment liquid can be suppressed. Example 3 The blending ratio of anionic surfactant and cationic surfactant was 60:40 (weight ratio), and the total of both was
A composition containing 20 parts by weight of a silicone antifoaming agent (using Dow Corning product FSX-001) per 100 parts by weight was dissolved in industrial tap water to determine the concentration.
A 120 ppm (by weight) solution was prepared. The anionic surfactant used here is C ₁₁ H ₂₃ COOCH ₂ O (CH ₂ CH ₂ O) _o SO ₃ Na (average value of n is 4), and the cationic surfactant is the following A ~
Either H. When the foaming of the above solutions was measured at 25° C. using the Ross-Miles method, the foam height immediately after dropping was zero for all solutions. After immersing and stirring 618 g of wet granulated slag (moisture content 19.1%) (500 g in dry weight) in 500 g of any of the above solutions at 25°C for 2 minutes,
It was air-dried in the same manner as in Example 1. The pH of the solution after treating the slag was within the range of 9.0 to 9.2. For comparison, 618 g of the above wet granulated slag was added to 500 g of industrial tap water with no surfactant added for 25 minutes.
After being immersed and stirred at ℃ for 2 minutes, it was simultaneously air-dried at room temperature in the same manner (experiment number). The pH of tap water after treating the slag was 9.1. The room temperature during air drying was kept at 25-15°C. The moisture content of the slag 1 hour and 54 hours after the start of air drying was measured in the same manner as in Example 1. Table 4 shows the obtained fruits.

[Table] From the above results, it can be seen that according to the present invention, dehydration and drying of slag can be significantly accelerated, and foaming of the treatment liquid can be suppressed. Example 4 As a cationic surfactant

Using [formula], C ₂₀ H ₄₁ O as anionic surfactant
(CH ₂ CH ₂ O) _o SO ₃ Na (average value of n is 10) was used. A mixture of both at a ratio of 60% by weight of anionic surfactant and 40% by weight of cationic surfactant.
Silicone antifoaming agent (Dow) per 100 parts by weight
A composition containing 40 parts by weight of FSX-001 (a Corning product) was added to the circulating water of a granulated slag manufacturing system at a certain steel mill (this circulating water is rich in Cl, SO ₄ ^2- , etc.).
PH is 9.5. ) to a concentration of 9 ppm (weight) to prepare a treatment solution. On the other hand, for comparison, the above cationic surfactant
A composition containing 40 parts by weight of the silicone antifoaming agent per 100 parts by weight was added to the circulating water at a concentration of 98 ppm.
(weight) to prepare a treatment liquid. Similarly, for comparison, the anionic surfactant was added to the circulating water at a concentration of 70 ppm (by weight), and the silicone antifoaming agent was added to the circulating water at a concentration of 28 ppm.
(weight) to prepare a treatment solution (Note: It was not possible to prepare a thick emulsion by mixing the two.) Immediately after preparing the above treatment liquid, foaming was measured at 25°C using the Ross-Miles method, and the foam height of the treatment liquid was zero, but the foam height of the treatment liquid was
It was 25mm. However, the treatment solution became foamy over time, and one month after preparation, the foam height measured by the Ross-Miles method reached 20 mm. On the other hand, the treatment liquid did not foam even after the passage of time. When a concentrated emulsion of the above cationic surfactant/anionic surfactant/antifoaming agent mixture (mixing ratio is the same as above) is prepared, and this emulsion is stored for 3 months and then used to prepare a processing solution. However, the foam height determined by the Ross-Miles method was zero. However, if a concentrated emulsion of the above cationic surfactant/antifoaming agent mixture (mixing ratio is the same as above) is prepared and this emulsion is stored before being used for preparing a processing solution, as the emulsion storage period becomes longer, , the foaming became intense immediately after the treatment solution was prepared. Therefore, when a cationic surfactant and an antifoaming agent are blended, foaming can be suppressed immediately after blending, but foaming gradually becomes more intense as time passes. After immersing and stirring 601 g of wet granulated slag (moisture content 16.8%) (500 g in dry weight) at 25°C for 2 minutes in 500 g of any of the above treatment solutions,
It was air-dried in the same manner as in Example 1. The pH of the solution after treating the slag was 9.5. For comparison, 601 g of the above wet granulated slag was added to the above circulating water to which no surfactant was added at 25°C.
After being immersed and stirred for a minute, it was simultaneously air-dried at room temperature in the same manner (experiment number). The pH of the circulating water after treating the slag was 9.5. The room temperature during air drying was kept at 25-15°C. 50 hours after the start of air drying, the sample slag in the colander was mixed until uniform, and then the moisture content of the slag was measured using an infrared moisture meter. The results are shown in Table 5.

[Table] No change over time was observed in the dehydration promoting performance of the treatment solution. Example 5 The blending ratio of anionic surfactant and cationic surfactant was 55:45 (weight ratio), and the total of both was
A composition containing 20 parts by weight of a silicone antifoaming agent (using Dow Corning product FSX-001) per 100 parts by weight was dissolved in the circulating water of the same granulated slag production system used in Example 4 to determine the concentration. A 90 ppm (by weight) solution was prepared. The anionic surfactant used here is C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) _o SO ₃ Na (average value of n is 3), and the cationic surfactant is one of the following A to C. . When the foaming of the above solutions was measured by the Ross-Miles method at 25°C, the foam height immediately after dropping was zero for all solutions. After immersing and stirring 618 g of wet granulated slag (water content 19.1%) (500 g in dry weight) at 25°C for 2 minutes in 500 g of any of the above solutions,
It was air-dried in the same manner as in Example 1. The pH of the solution after treating the slag was 9.5. For comparison, 618 g of the wet granulated slag was immersed and stirred at 25° C. for 2 minutes in 500 g of the circulating water to which no surfactant was added, and then air-dried at room temperature in the same manner. PH of circulating water after processing slag
was 9.5. The room temperature during air drying was kept at 25-15°C. The moisture content of the slag 56 hours after the start of air drying was measured in the same manner as in Example 4. The results obtained are shown in Table 6.

[Table] Example 6 A composition consisting of 55% by weight of an anionic surfactant and 45% by weight of a cationic surfactant was dissolved in industrial tap water to prepare a solution having a concentration of 100 ppm (by weight). The anionic surfactant used here is C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) _o SO ₃ Na (average value of n is 6), and the cationic surfactant is one of the following A to C. . A [C ₁₄ H ₂₉ N(CH ₃ ) ₃ ] ⁺ Cl B C ₁₁ H ₂₃ CONHC ₂ H ₄ N(CH ₂ CH ₂ OH) ₂ acetate C C ₁₂ H ₂₅ N(CH ₂ CH ₂ OH) ₂ For comparison, a solution (experiment number) in which only the above anionic surfactant was dissolved at a concentration of 100 ppm (weight), and a solution in which only A of the above cationic surfactants was dissolved at a concentration of 100 ppm (weight) A solution (experiment number) was prepared. Foaming of these solutions was measured by the Ross-Miles method. Into 500 g of any of these solutions, 613 g (500 g in terms of dry weight) of wet granulated slag (water content 18.4%) was immersed and stirred at 25°C for 2 minutes, and then the same procedure as in Example 1 was carried out. and air dried. The pH of the solution after treating the slag was within the range of 9.0 to 9.2. For comparison, 613 g of the above wet granulated slag was added to 500 g of industrial tap water with no surfactant added.
After being immersed and stirred at ℃ for 2 minutes, it was simultaneously air-dried at room temperature in the same manner (experiment number). The pH of the tap water after treatment was 9.1. The room temperature during air drying was 30-20°C. The moisture content of the slag 6 hours and 48 hours after the start of air drying was measured in the same manner as in Example 1. Table 7 shows the measurement results of the foaming of the solution and the water content of the slag.

[Table] Example 7 A composition consisting of 60% by weight of an anionic surfactant and 40% by weight of a cationic surfactant was dissolved in the same circulating water of the granulated slag production system used in Example 4 to give a concentration of 100 ppm (by weight). ) solution was prepared. The anionic surfactant used here is C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) _o SO ₃ Na (average value of n is 4), and the cationic surfactant is one of the following A to C. . The foaming of these solutions was measured using the Ross-Miles method.
Measured at °C. After immersing 618 g (500 g in dry weight) of wet granulated slag (moisture content 19.1%) in 500 g of any of these solutions at 25°C for 2 minutes and stirring,
It was air-dried in the same manner as in Example 1. The pH of the solution after treating the slag was 9.5. For comparison, 618 g of the above wet granulated slag was added to 500 g of the above circulating water to which no surfactant was added at 25°C.
After immersing and stirring for 2 minutes, the sample was simultaneously air-dried at room temperature in the same manner (experiment number). The pH of the circulating water after treating the slag was 9.5. The room temperature during air drying was 25-15°C. 64 hours after the start of air drying, the moisture content of the slag was measured in the same manner as in Example 4. Table 8 shows the measurement results of the foaming of the solution and the water content of the slag.

[Table] (c) Effects of the Invention According to the present invention, dehydration or drying of water-wet granulated slag is promoted. Therefore, even if the water-wet granulated slag is naturally dried in a thickly deposited state, the water content of the granulated slag can be lowered compared to the conventional level. In particular, it becomes possible to dry the granulated slag to a moisture content of 4% or less only by natural drying, and it is possible to eliminate the need for heating and drying the slag before using it as a cement raw material. Moreover, the foaming power of the liquid used for the slag dehydration promotion treatment is reduced, and it is possible to substantially prevent foaming. Moreover, even if the antifoaming agent is mixed with a surfactant in advance and then used for dehydration promotion treatment,
The treatment agent of the present invention has the advantage that the foam suppressing effect is maintained for a long period of time.

Claims (1)

[Claims] 1 (a) The following formula RO−(CH ₂ CH ₂ O)− _o SO ₃ M … (Formula 1) or RCOOCH ₂ O−(CH ₂ CH ₂ O)− _o SO ₃ M…(Formula 3) (However, in the above formula, R has 11 carbon atoms.
~30 monovalent hydrocarbon group, R' is an H atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms. M is H ⁺ ,
Na ⁺ , K ⁺ , NH ₄ ⁺ , 1/2Mg ²⁺ , 1/2Ca ²⁺ or monovalent organic cations having 10 or less carbon atoms. The average value of n is 3-20. ) one or more selected from the group consisting of anionic surfactants represented by any of the following: (b) at least one carbon atom in the molecule of 11 to
one or more selected from the group consisting of cationic surfactants having 30 monovalent hydrocarbon groups, and 79 to 23% by weight of the above anionic surfactant, based on the total of both A dehydration accelerating treatment agent for granulated slag, characterized by containing a cationic surfactant in a proportion of 21 to 77% by weight. 2. The processing agent according to claim 1, which contains an antifoaming agent. 3. The processing agent according to claim 2, wherein the antifoaming agent is a silicone antifoaming agent.