KR0155061B1 - Chemical crushing agent containing hydration retarder - Google Patents

Abstract

The present invention is to provide a hydration retardant for a non-explosive crushing agent used for the crushing of rock or the dismantling of concrete structures.

The present invention provides zinc sulfate [ZnSO ₄ .XH ₂ O, X = 0 to 7], zinc nitrate [Zn (NO ₃ ) ₂ .XH ₂ O, X = 0 to 6], copper sulfate [CuSO ₄ .XH ₂ O, X = 0 to 5] or copper nitrate [Cu (NO ₃ ) ₂ .XH ₂ O, X = 0 to 6] to provide a hydration retardant for a non-explosive crushing agent selected from the group consisting of:

The hydration retarder of the present invention excels in initial hydration retardation and quantitatively controls the rate of hydration because there is a linear relationship (t = K1 + K2log x) between the amount added and the reaction time.

Description

Hydration Retardant for Non-Oxidic Shredding Agent

The present invention relates to a hydration retarder for a non-explosive crushing agent that controls the rate of hydration reaction of the crushing agent. More specifically, the present invention relates to a hydration retardant for non-explosive crushing agents selected from sulfates or nitrates of copper and zinc which excel in initial hydration retardation and quantitatively retard hydration rates.

In recent years, for crushing rock or dismantling concrete structures, non-explosive crushing agents which can be statically crushed by replacing explosives such as dynamite have been widely used. This non-explosive crushing agent is a powder mainly composed of free lime, which is mixed with a predetermined amount of water to form a slurry, and then injected into the perforated body of the crushed body.

Water-containing shredder slurry undergoes hydration of glass lime with exotherm, produces calcium hydroxide as a reaction product, and at the same time, volume expansion occurs to generate expansion pressure that pushes the perforated sidewall of the shredded body. Dismantle the sieve. By using such a non-explosive crushing agent, it was possible to employ a safe and pollution-free dismantling method.

Non-explosive crushing agents should satisfy the following characteristics. First, more than a certain level of expansion pressure must be expressed within a predetermined time. Second, after injection of the shredder slurry into the perforations, iron scraping out of the shredder should not occur. Third, the slurry made by mixing the crushing agent and the mixed water should maintain fluidity until about 10 to 15 minutes, which is the time required to inject into the perforation.

As described above, the non-explosive crushing agent utilizes the hydration reaction of the glass lime, and the hydration reaction rate of the glass lime is very temperature dependent. Therefore, it is essential to control the hydration activity differentially depending on the conditions of use, non-explosive crushing agent is usually produced by the season for winter, spring and summer for large diameter and small diameter depending on the perforation diameter.

The method for controlling the hydration activity of the non-explosive crushing agent is as follows.

First, there is a method of controlling the hydration activity of the krinka itself. By adjusting the compounding composition and the firing method of the raw materials, various kinds of krinka having different hydration activities of the krinka itself are prepared, and additives such as grinding and fluidizing agents are added to prepare crushing agents according to caliber and season.

The demand for non-explosive crushers is generally limited. When manufacturing various kinds of krinka with specific hydration activity according to seasons and calibers, there is a drawback that the production efficiency is low and the manufacturing cost is increased because a typical multi-quantity production system is required. have.

Second, there is a method using a hydration retarder. Since the production of one kind of krinka having proper hydration activity is unified, there are advantages such as improvement of production efficiency and cost reduction compared to the first method. Therefore, it can be said that the hydration retarder technology is very important in the preparation of non-bomb crushing agent.

Hydration retardants for the production of non-explosive crushers are known as follows.

a) sugars such as gluconic acid and gluconic acid salts, sugar, sorbitol, and mannitol

b) organic acids such as citric acid and citric acid salts, tartaric acid and tartaric acid salts;

c) boric acid series such as boric acid and boric acid salts

d) silofluoride series such as Na ₂ SiF ₆ , K ₂ SiF ₆ , MgSiF ₆ , ZnSiF ₆

e) Fluoride series such as KF and NaF

In the above hydration retarder, the saccharide series delays the hydration of the free lime when added to a certain amount, but has a disadvantage in that it promotes hydration inversely when added to the above amount. In addition, the organic acid series delays the hydration when added to a certain amount, but there is no delay effect even when added in a larger amount. On the other hand, silica fluorides retard the hydration of glass lime very sensitively depending on the amount of addition, and when added more than a certain amount, it is very delayed and the expansion pressure of the crushing agent is extremely low, and Na ₂ O and K ₂ O in the krinka Hydration delay is greatly affected by alkali content. Due to its low dissolution rate, boric acid series has poor initial hydration retardation, resulting in very high fluidity loss of the crusher slurry made by mixing the crusher and water, and the degree of hydration delay of glass lime is limited to a certain level. Fluoride salts have a disadvantage that the degree of hydration delay is very sensitive depending on the amount of addition, such as silica fluoride.

That is, the hydration retardation agent described above is non-linear, so the hydration delay of the glass lime is not linear, so quantitative hydration control is not possible. Very difficult to do.

The present invention is to solve such a problem in the prior art, there is provided a hydration retardation agent for a non-explosive crushing agent capable of quantitative hydration control because there is a good initial delay of the hydration reaction and there is a linear relationship between the addition amount and the reaction time Its purpose is to.

Hereinafter, the present invention will be described in detail.

The present invention provides zinc sulfate [ZnSO ₄ .XH ₂ O, X = 0 to 7], zinc nitrate [Zn (NO ₃ ) ₂ .XH ₂ O, X = 0 to 6], copper sulfate [CuSO ₄ .XH ₂ O, X = 0 to 5] or copper nitrate [Cu (NO ₃ ) ₂ .XH ₂ O, X = 0 to 6].

Hereinafter, the present invention will be described in more detail.

The present invention is a hydration retardant for a non-explosive crushing agent selected from the group consisting of zinc sulfate, copper sulfate, zinc nitrate or copper nitrate.

In addition, the hydration retardation agent of the present invention is characterized by adding 0.2 to 3.2 parts by weight based on 100 parts by weight of the Krinka powder of the non-explosive crushing agent.

The non-explosive crushing agent manufacturing method is as follows.

In a first step, a krinka is produced by firing a combination raw material made by adding and pulverizing a small amount of a raw material having a calcined raw material and other components as a main raw material at a high temperature. In step 2, the clinker is pulverized into an appropriate powder to obtain a powder state. In step 3, a crushing agent is prepared by adding and mixing additives such as a fluidizing agent, a hydration retardant, or a hydration accelerator, to the krinka powder.

The process of delaying the hydration of zinc sulfate, zinc nitrate, copper sulfate or copper nitrate in the non-explosive crushing agent is as follows.

In the first step, zinc sulfate, zinc nitrate, copper sulfate, and copper nitrate are dissolved in water and dissociated in ionic state.

In the second step, Zn (+2) or Cu (+2) ions produced by dissociation of Ca (+2) ions eluted from glass lime and retarder, OH (-1) ions produced by dissociation of water, and H ₂ O and the like that do not dissociate react to form Ca [Zn (OH) ₃ H ₂ O] or Ca [Cu (OH) ₃ H ₂ O] _{2, which} is poorly soluble, which covers the surface of the glass lime. Delay hydration.

The coating thickness of Ca [Zn (OH) ₃ · H ₂ O] or Ca [Cu (OH) ₃ · H ₂ O] ₂ increases proportionally with the addition of these retardants and the hydration reaction point (t) of free lime The relationship between t = k1 + k2log x is established between the addition amount (x) and the constant value (k), and a linear relationship exists between the addition amount of the retardant and the time point of free lime reaction. By the use of these retardants, the hydration of the glass lime can be controlled quantitatively, and therefore, it is easy to manufacture various kinds of crushing agents of different diameters and seasons having different hydration activities using one kind of krinka.

[Production example and test example]

2 parts by weight of iron raw material is mixed with 98 parts by weight of limestone, and the mixture is pulverized to 10% of 88μ residue using a laboratory ball mill, and then a suitable amount of water is added to a diameter of about 1 cm, which is 200 ° C. It is dried for 4 hours in a drying furnace. The molded and dried combination raw materials were calcined using a laboratory electric furnace, decarbonated at 1000 ° C. for 1 hour, and then calcined at 1450 ° C. for 1 hour to prepare a non-explosive crusher clinker. The chemical composition of this Krinka is shown in Table 1 below, and the content of free lime is 80.2%.

This krinka was pulverized using a laboratory ball mill to make 20% of the 88 μg residue, to make krinka powder, and Mighty-100 and various reagent grade retardants of Dongyang M.K Co., Ltd. were added thereto as a fluidizing agent to prepare a non-explosive crushing agent. 200 g of crushing agent and 60 g of water at 20 ° C. were mixed for 1 minute to cure the crushing agent slurry, and the hydration reaction controllability of various retardants was evaluated by measuring the slurry temperature, fluidity, and slurry hydration reaction time immediately after mixing. The hydration reaction time was measured as the time elapsed until the slurry made in the laboratory adjusted to 20 ° C reached 100 ° C after the crushing slurry made by mixing with water was placed in a paper cup.

Example 1

Hydration Control of Zinc Sulfate and Zinc Nitrate

0.2 to 3.2 parts by weight of zinc sulfate or zinc nitrate were added as 100 parts by weight of the Krinka powder and 1 part by weight of the fluidizing agent to evaluate the hydration reaction controllability.

When sulphate and nitrate were added, the initial hydration retardation was excellent, so that the slurry temperature immediately after mixing was low and the fluidity of the slurry was also excellent. When the hydration reaction time was t, the amount of zinc sulfate added x1, and the amount of zinc nitrate added x2, there was a relationship of t = 271 + 259.1log x1 and t = 245 + 232.2log x2, enabling quantitative hydration control.

Example 2

[Controlability of Copper Sulphate and Copper Nitrate Hydration Reactions]

100 parts by weight of the Krinka powder and 1 part by weight of the fluidizing agent were added 0.2 to 3.2 parts by weight of copper sulfate or copper nitrate as the hydration retardant to evaluate the hydration reaction controllability as shown in Tables 4 and 5.

When sulphate and copper nitrate were added, the initial hydration retardation was excellent, so that the slurry temperature immediately after mixing was low, and the slurry fluidity was also excellent. When the hydration reaction time was t, the amount of copper sulfate added x3 and the amount of copper nitrate added x4, there was a relationship of t = 255 + 216.6 log x1 and t = 184 + 169.8log x2, which allowed quantitative hydration control.

Example 3

[Production of Non-Explosive Crushing Agent and Evaluation of Inflation Pressure]

A crushing agent was prepared using zinc sulfate as a powder having 20% of 88μ residue, mighty-100 and hydration retardant. The inflation pressure was measured by mixing 100 parts of crushing agent and 30 parts of 20 ° C water, injecting into a steel pipe with a strain gauge and curing in a constant temperature water bath adjusted to 20 ° C. The steel pipe for measuring the inflation pressure was formed by welding a steel plate having a thickness of 3.2 mm with one hole to a steel pipe for pressure piping having an outer diameter of 48.6 mm, an inner diameter of 38.4 mm, and a length of 200 mm.

By adding 0.2% or more of zinc sulfate, it was possible to prepare a non-explosive closure agent having a high expansion pressure compared to no addition and excellent flowability of the slurry.

Comparative Example 1

[Control of Hydration Reaction of Sodium Gluconate and Sulta]

The hydration reaction controllability was evaluated by adding 0 to 1.6 parts by weight of soda gluconate and sugar as a hydration retardant to 100 parts by weight of the krinka powder and 1 part by weight of the fluidizing agent.

When 0.4% or more of sodium gluconate and sugar were added, the hydration reaction was accelerated rapidly, and when 0.2% or less or 0.8% or more was added, the initial hydration delay was poor, resulting in poor slurry fluidity immediately after mixing.

Comparative Example 2

[Control of Hydration Reaction of Citric Acid and Sodium Tartrate]

The hydration reaction controllability was evaluated by adding 0.1 to 1.6 parts by weight of sodium citrate and sodium tartarate as a hydration retardant to 100 parts by weight of the Krinka powder and 1 part by weight of the fluidizing agent.

Sodium citrate and sodium stannate delayed the hydration reaction up to about 0.8%, but the addition of 0.8% or more did not show a significant delay effect, and the hydration reaction time was generally short. If the addition amount was 0.4% or less, the fluidity of the slurry was poor.

Comparative Example 3

[Control of Hydration Reaction of Sodium Fluoride]

100 parts by weight of the Krinka powder and 1 part by weight of the fluidizing agent were added 0.05 to 0.8 parts by weight of sodium silicate as a hydration retardant to evaluate the hydration controllability as shown in Table 11 below.

The hydration reaction was sensitively delayed depending on the amount of sodium silica fluoride. When 0.8% was added, the hydration reaction was delayed so that the slurry temperature did not reach 100 ° C. It was generally good.

[Comparative Example 4]

[Hydration Reaction Controllability of Boric Acid]

The hydration reaction controllability was evaluated by adding 0.1 to 1.6 parts by weight of boric acid as a hydration retardant to 100 parts by weight of the krinka powder and 1 part by weight of the fluidizing agent.

Depending on the amount of boric acid added, the degree of hydration delay was relatively small, and the initial hydration delay was poor, and the slurry temperature immediately after mixing was high, and the fluidity of the slurry was also poor.

[Comparative Example 5]

[Control of Hydration Reaction of Sodium Fluoride]

The results of evaluating the hydration reaction controllability by adding 0.05 to 0.8 parts by weight of sodium fluoride as a hydration retardant to 100 parts by weight of the Krinka powder and 1 part by weight of the fluidizing agent are shown in Table 13.

The hydration reaction was sensitively delayed depending on the amount of sodium fluoride added, and the hydration reaction time could not be measured because the hydration reaction was delayed more than 0.4% and the slurry temperature did not reach 100 ° C. The fluidity was good.

Claims (2)

Zinc sulfate [ZnSO ₄ ㆍ XH ₂ O, X = 0 to 7], zinc nitrate [Zn (NO ₃ ) ₂ ㆍ XH ₂ O, X = 0 to 6], copper sulfate [CuSO ₄ ㆍ XH ₂ O, X = 0 To 5] or a copper nitrate [Cu (NO ₃ ) ₂ .XH ₂ O, X = 0 to 6]. The hydration retardant for a nonaqueous crushing agent according to claim 1, which is comprised in an amount of 0.2 to 3.2 parts by weight with respect to 100 parts by weight of the Krinka powder of the nonaqueous crushing agent.