KR100663882B1 - Modified sulfur mortar utilizing modified sulfur and waste materials for repairing and reinforcing, and its manufacturing method - Google Patents

Abstract

Mortar containing modified stable sulfur composition as by-product of oil refinery is provided to show superior early strength, adhesiveness and long term durability effective to repair and reinforce concrete structure when the structure is coated with the mortar. Mortar consist of the modified sulfur composition with waste fine powder and waste aggregate. The mortar includes 30-90wt.% of modified sulfur polymer, 5-65wt.% of inorganic waste material and 0.1-1wt.% of a foaming agent to inhibit generation of foam. The inorganic waste material is selected from waste microfine powder, fly ash, slag, quartz fine powder and silica fume. The modified sulfur polymer is prepared by reacting industrial sulfur byproduct with dicyclo pentadiene and oligomer. The mortar is formed by the steps of: preparing a slurry containing the modified sulfur polymer and the inorganic waste material; adding 0.1-1wt.% of the foaming agent to the slurry; spraying the slurry mixture on the surface of a subject to be coated by a sprayer pre-heated at 120 to 180deg.C; and naturally cooling and curing the subject.

Description

Modified sulfur mortar for reinforcement using reformed sulfur and waste resources, and its manufacturing method {MODIFIED SULFUR MORTAR UTILIZING

1 is a flow chart showing a manufacturing process of building materials according to the present invention.

Figure 2a is a photograph of the modified sulfur thin film coated on the mortar surface according to the present invention.

Figure 2b is a photograph of a modified sulfur thin film coated on a wooden surface according to the present invention.

Figure 2c is a photograph of a modified sulfur thin film coated on the metal surface according to the present invention.

3 is a photograph of a modified sulfur thin film coated on a metal surface according to the present invention.

Figure 4 is a photograph showing the appearance of the "angle" test specimens appear after the chemical "erosion resistance" test.

Figure 5 is a photograph showing the appearance after immersion of concrete specimens immersed in 5% HCl solution.

FIG. 6 is a graph showing the weight change rate according to the immersion period with respect to concrete specimens immersed in 5% HCl solution.

The present invention relates to reformed sulfur mortar for reinforcing reinforcement using reformed sulfur and waste resources, and a method for producing the same. Particularly, a modified reformed sulfur composition is prepared by synthesizing recovered sulfur which is a by-product of an oil refinery. The present invention relates to a modified sulfur mortar for reinforcing reinforcing reinforcing reinforcing reinforcing and chemicals having excellent resistance to chemicals by mixing waste materials in a very short time.

Currently, building materials in Korea use as much amount as possible to recycle various waste materials generated at industrial sites as raw materials. In order to promote the use of such eco-friendly recycled materials, the government has sought to promote eco-friendly product purchase. Law, "the government will enforce the mandatory purchase of 20% of purchased products.

On the other hand, in domestic refineries, a large amount of sulfur is generated when refining crude oil, and some of them are consumed in fertilizer plants, but they are being handled by a large amount of inventory processing.In the petrochemical plant, RPG (row pyrolysis gasoline) Although it contains a large amount of oligomers for dicyclo pentadiene (DCPD), it is being burned to the atmosphere due to lack of economic efficiency.

In addition, a large amount of waste concrete is generated at the construction site, and a large amount of waste aggregates and waste powders are generated when crushing and classifying waste intermediate treatment companies. Recently, in order to reuse the waste powders as cement raw materials, recently used waste powders are used at high temperature. Related studies have been published as a method of converting hydrated Ca (OH) ₂ to CaO by heat treatment.

On the other hand, the Ministry of Construction and Transportation established the "Concrete Standard Specification Durability" to evaluate the durability of concrete structures by adopting the durability provisions included in the concrete standard specifications. The scope and method of durability assessment for freezing, thawing, chemical erosion and alkali aggregate reactions are specified. Most of the degradation of concrete is caused by chemical reaction, and the most common corrosion is caused by salting or neutralization of concrete structure. Especially, concrete structure exposed to salty environment is a problem that early degradation due to corrosion of steel is a big problem. It is emerging.

On the other hand, according to the "Chemical Erosion and Elution Research Institute Committee" of the Japanese Society of Civil Engineers, the sewage facility reports that sulfuric acid is generated by the action of microorganisms and concrete is eroded and degraded. In other words, sulphate in sewage or wastewater is converted to hydrogen sulfide by the action of sulfate reducing bacteria in anaerobic atmosphere such as a sealed reservoir, and finally oxidized to sulfuric acid by sulfated bacteria. The surface is whitened and more deteriorated areas are easily peeled off to expose aggregates and rebars. In addition, many manufacturing industries, including chemical plants, are eroding concrete due to the use of many types of explosives.

In order to prevent deterioration and repair of concrete, concrete protective coatings are used to classify them into two types: synthetic resins such as epoxy and cements mixed with reemulsified resins in cement. If repeated, it implies problems such as water repellent waterproofing performance and environmental pollution due to emulsion deterioration, and cement system has problems such as cracking and water leakage due to volume expansion of concrete structure by hydration reaction. In the field where long-term chemical resistance to strong acid alkali is required in the thermal power plant, such as wastewater treatment plant, it is incomplete with resin material, so the construction is carried out by stacking glass mats or carbon mats in multiple layers. Material cost It has become a burden on the.

An object of the present invention is to provide a reinforcing mortar material that can exhibit excellent physical properties in terms of resistance and strength to chemicals while using waste.

Another object of the present invention is to provide a modified sulfur mortar for reinforcing reinforcement which can be easily coated on concrete surfaces, metals and wood, and the like and a method of manufacturing the same.

Etc. Other objects and features of the present invention will be presented in more detail in the following detailed description.

In order to achieve the above object, the present invention provides a reformed sulfur reforming mortar consisting of 30-90% by weight of modified sulfur polymer, 5-65% by weight of substrate-free waste material, and 0.1-1% by weight of antifoaming agent.

The inorganic waste material is preferably at least one selected from waste fine powder, fly ash, slag, silica powder and silica fume.

In the present invention, 'composition' refers to the content of other components added when the total weight of the modified sulfur polymer and the inorganic waste material mixture (or the slurry including the mixture) is 100%.

The present invention also comprises the steps of preparing a slurry by melting 30 to 90% by weight of the modified sulfur polymer and 5 to 65% by weight of the inorganic waste material within the temperature range of 120 ℃ to 180 ℃; Mixing the slurry with a pre-heated antifoaming agent in a temperature range of 120 ° C. to 180 ° C. at 1-10% by weight and 0.1-1% by weight, respectively; Spraying the slurry mixture on the surface of the coating body by using a preheated spray within a temperature range of 120 ° C to 180 ° C; It provides a method for producing a reforming sulfur reforming mortar, characterized in that consisting of the step of naturally cooling and curing the coating body at room temperature.

In the present invention, the reformed sulfur composition uses a reformed sulfur polymer composition obtained by reacting DCPD (dicyclo pentadiene; dicyclopentadiene) with an oligomer in sulfur discharged as a by-product from an oil refinery.

Specifically, the modified sulfur polymer is a mixture of cyclopentadiene oligomer and dicyclopentadiene in a volume ratio of 50:50, and the mixture is mixed with sulfur at 5 vol% based on 100 vol% of sulfur and at high temperature (eg For example, at 120 ° C. to 180 ° C.). If necessary, the synthesized reformed sulfuric acid may be cooled to room temperature and stored in a flake state, and then melted at 130 ° C. if necessary.

The inorganic waste material used in the present invention is not particularly limited as long as it has particles and specific gravity that can be sprayed from the sprayer, but industrial waste is preferably used. Industrial wastes include, for example, waste aggregates and waste fines from waste concrete, fly ash from the power and general industries, slag from the steel industry, silica fines from silica, and waste fines from waste mines. One or more types selected can be mentioned. In particular, in the embodiment of the present invention, the waste powder, fly ash and silica powder.

The fly ash refers to the fine powder discharged after burning the coal ash in the power industry and the heating furnace, the main component is composed of silica (SiO ₂ ), alumina (Al ₂ O ₃ ), calcium oxide (CaO) and the like, and fine particle structure Is an oxide added in the form of round or oval and added to improve the fluidity of concrete. It can be used if it has been used in concrete or construction materials since the past. The preferred amount of fly ash added to achieve good spraying and coating results in the spray is 25-50% by weight. When fly ash is added more than 50% by weight, the spraying state is not spread evenly but is thickly sprayed, and the attached surface is irregular.When it is added less than 20% by weight, the spraying state is not different but it flows down even after sticking. This happens.

The waste powder refers to waste powder generated from waste concrete, but is not particularly limited as long as the powders generated from waste mine or silica are used.

The silica powder is used in the examples of the present invention because fly ash and waste powder are waste raw materials, but are excellent in terms of raw materials having relatively high prices and wear rates. Considering the spraying ability of the spray and the state of the coated surface, the preferred amount of addition is 20 to 40% by weight. In the batch combination that is out of the added amount, the same number of phenomena as in the case of adding fly ash occurred, and if the particle size of the silica sand powder is small as about 10 μm or less, the viscosity of the modified sulfur mortar increases even if it is less, resulting in poor workability. And it was found that the price competitiveness is also disadvantageous.

In addition, an antifoaming agent may be additionally added to the slurry in which the modified sulfur polymer composition and the fine powder are mixed to suppress foaming. A preferred amount is 0.1-1% by weight in addition to the total weight of the slurry. This is to remove the bubbles in the slurry that may occur to increase the density of the cured slurry to maintain a dense structure after curing.

Referring to the flowchart of FIG. 1, a method for preparing a reformed sulfur reforming mortar comprising the reformed sulfur composition, waste materials, and an additional antifoaming agent will be described.

Sulfur obtained as a by-product in an industrial site, dicyclopentadiene, and a modified sulfur polymer obtained by reacting an oligomer are melted in an inorganic waste material within a temperature range of 120 ° C to 180 ° C to maintain a slurry state. The antifoaming agent preheated in the temperature range of 120 ℃ ~ 180 ℃ is added to the slurry and mixed. The slurry mixture is sprayed onto the surface of the coating body to be coated by using a preheated spray or the like within a temperature range of 120 ° C to 180 ° C. Finally, the coating body is naturally cooled and cured at room temperature.

Maintaining a temperature range of 120 ° C. to 180 ° C. in all the above processes may adversely affect physical properties such as workability or strength and adhesion when the temperature range is out of range. When the temperature range is low, the spraying force decreases and a lot of bubbles occur. When the temperature range is high, the viscosity suddenly increases, and the workability is lost, and when time passes, the rubber becomes hard (rubber like). This can occur and be fatal to the injector itself. More preferably, the temperature range is maintained at 120 ℃ ~ 140 ℃ it is advantageous in terms of economic efficiency or workability.

The coating body is preferably preheated and maintained at a temperature of 120 ° C to 180 ° C, but in view of the harsh conditions in the field, it is not a big problem to attach even when sprayed without preheating, and in a rainy environment, which is a more harsh environment, In view of this, even if the coating body is sprayed in the wet state, it does not become a problem in the adhesion surface.

Hereinafter, examples and comparative examples will be described in detail with reference to the drawings, but these examples and comparative examples are only presented to more clearly understand the present invention and are not intended to limit the scope of the present invention. The present invention will be defined only within the scope of the technical idea of the claims to be described later.

Referring to the embodiment prepared according to the above-mentioned manner as follows.

Example 1

70 g of the modified sulfur composition and 30 g of waste fine powder were mixed in the hopper of the spray gun, 0.5 g of the antifoaming agent was mixed again in the slurry melted at a temperature range of 120 ° C. to 130 ° C., and then mixed by a mobile impeller mixer for about 2 minutes. Adhesion strength was measured by applying it on a 70 mm × 70 mm × 20 mm mortar test piece using an air pressure preheated at a pressure of about 2-4 kg / cm 2 and a temperature of 150 ° C. to 180 ° C.

At this time, the test method was conducted based on KS F 4726 (cement-based base material), and the size of aggregate (fine powder) was used to pass almost 0.6mm of sieve specified in KS F 2502.

The coating body is molded in accordance with KS L 5105 in a 70mm × 70mm × 20mm standard, cured for 1 day in a constant temperature and humidity chamber in which a temperature of 20 ± 3 ° C. and a humidity of 80% or more is maintained, followed by demolding. It was cured for 14 days in water maintained at a temperature of 20 ± 3 ℃ was used as a test base plate.

Example 2

Under the same conditions as in Example 1, experiment was performed by mixing 30 g of silica sand powder instead of waste powder.

Example 3

Under the same conditions as in Example 1, the experiment was carried out by mixing 30 g of fly ash in place of waste fine powder.

Example 4

70 g of the reformed sulfur composition and 30 g of waste fine powder were mixed in the hopper of the spray gun, and 0.5 g of the antifoaming agent was mixed again in the slurry melted in the temperature range of 120 ° C. to 130 ° C., followed by mixing for about 2 minutes using a mobile impeller mixer. Adhesion strength was measured by applying a pressure of about 2-4 kg / cm 2 and air pressure preheated from 150 ° C. to 180 ° C. on a 70 × 70 × 20 mm wood test piece.

 At this time, the test method was carried out according to KS F 4726. The size of aggregate (fine powder) was used to pass almost 0.6mm of the sieve specified in KS F 2502, and the wood coating body was kept without curing. After drying for about a week in the test was used as a base plate.

Example 5

Under the same conditions as in Example 4, the experiment was carried out by mixing 30 g of silica sand powder instead of waste powder.

Example 6

Under the same conditions as in Example 4, the experiment was carried out by mixing 30 g of fly ash in place of waste fine powder.

Example 7

Under the same conditions as in Example 1, the coating body was used as a metal test piece manufactured in a 70mm × 70mm × 20mm standard.

Example 8

Under the same conditions as in Example 7, the experiment was carried out by mixing 30 g of silica fine powder instead of waste fine powder.

Example 9

Under the same conditions as in Example 7, it was tested by mixing 30g fly ash instead of waste fine powder.

The modified sulfur thin film photographed on the mortar, wood, and metal specimens in relation to the above examples is shown in FIGS. 2A to 2C, and the experimental results according to the examples are shown in Table 1 below.

[Table 1] Experimental results Unit: weight%

Coating body Reformed sulfur Waste powder Quartz sand Fly ash Atomization Coating state Adhesion Strength (㎏ / ㎠) Example 1 mortar 70 30 Good Good 20       2 mortar 70 30 Good Good 27       3 mortar 70 30 Good Good 25 Example 4 wood 70 30 Good Good 8       5 wood 70 30 Good Good 12       6 wood 70 30 Good Good 10 Example 7 metal 70 30 Good Good 5       8 metal 70 30 Good Good 7       9 metal 70 30 Good Good 6

As can be seen from the results of the experiment shown in Table 1, it can be seen that the adhesion strength of the coating body is greater than that of the metal surface or the wood surface when the coating body is cement mortar. It can be seen that adhesion is better than ash or waste powder.

The spray and coated surface showed good overall results. Especially, the adhesion strength value of 27 kg / cm 2 was about 20-kg. It shows 25kg / cm 2 and shows relatively good results, considering that the properties of the domestically applied coatings show about 20kg / cm 2.

3 is a photograph of a modified sulfur thin film coated on a metal surface according to the present invention, it was confirmed that the surface coating state is good.

In addition, the modified sulfur mortar according to the present invention showed superior resistance in terms of chemical resistance than conventional coating materials. The reason why the modified sulfur mortar according to the present invention exhibits excellent chemical resistance is that the chemical solution is substantially reformed sulfur due to the fact that the absorption rate is almost zero due to the sulfur filling around the aggregate and the fine particles and the pores. It is believed that chemical resistance increases because it cannot penetrate the mortar surface.

The inventors produced the molded article using the modified sulfur mortar of the present invention and performed a chemical erosion resistance test on it. After about 6 months, the results of chemical and erosion resistance were confirmed. The modified sulfur mortar of the present invention showed no change in appearance or weight loss, but the concrete specimens using general mortar had a lot of changes in appearance or weight change. Fig. 4 shows after the chemical corrosion resistance test. This is how the test pieces look.

In FIG. 4, the two left and right test pieces were tested at 5% CaCl ₂ immersion solution, and the two left and right test pieces were tested at 5% Na ₂ SO ₄ immersion solution. The test pieces were tested in sea water, the left test pieces (labeled 2, 1, 4) are modified sulfur mortar test pieces according to the present invention, and the right test pieces are general mortar test pieces. The modified sulfur mortar test piece on the left can be easily distinguished by the naked eye. whereas regardless of all visible without apparent over the immersion solution type, plain mortar specimens on the right appear much apparent difference by dipping solution. in other words, while looking CaCl no longer only one test specimen at ₂ immersion solution, Na ₂ SO _{4 If} the specimen tested in the immersion solution is cracked and peeled over the entire surface of the specimen, It was difficult to handle the peeling test pieces so that they could fall off.

In general, as an erosion mechanism by sulfates such as Na ₂ SO ₄ , SO ₄ ^2- ions penetrate into the mortar hardened body through the pores to form gypsum by reaction with calcium hydroxide and finally ettringite is formed. This results in expansion failure due to an increase in the internal expansion pressure of the hardened body.

The test specimens tested in artificial seawater were eroded and separated from the surface of the fine eroded sediments on the front, so that they could not be washed away by the flowing water and the sharp brush. The erosion rate of concrete in this politic state and in a fluid state can be explained by the phenomenon of differently progressing.

That is, when the reaction product `` deposits '' on the surface of the specimen under the same politics as in the above experiment, the reaction area is reduced and the erosion is suppressed from the surface while the erosion reactant is removed from the surface while the erosion reacts. Therefore, it is much faster to erode. Sea water is relatively less corrosive than acid and sulfate, and calcium sulphate and magnesium sulfate in seawater are less corrosive but relatively less erosive in the seawater. ． Rather, one of the components of the seawater, which is a problem of chemical erosion of concrete, is magnesium chloride, which reacts with calcium hydroxide in the hardening body to produce calcium chloride, resulting in a significant increase in pore volume resulting in a decrease in strength. From the above results, depending on the type of immersion solution, the general mortar specimens were severely deformed, but the modified sulfur mortar specimens of the present invention did not show any significant deformation.

After the immersion of the concrete test specimens immersed in 5% HCl solution is shown in Figure 5. The upper test piece is a normal concrete test piece and the lower test piece is a concrete test piece using modified sulfur mortar of the present invention. Similarly, in general concrete specimens, the surface was irregularly corroded to the extent of piles and cracks occurred in the bottom and side surfaces. However, the specimen using modified sulfur mortar of the present invention showed almost no change in appearance or weight change rate.

The rate of change in weight according to the immersion period was shown in Fig. 6 for the concrete specimens immersed in 5% HCl solution. As can be seen from the figure, the general concrete began to decrease in weight after immersion. While the weight loss was 4.6%, after about 3 months, the weight loss rate was steadily decreasing at 66%, while the modified sulfur mortar test specimen of the present invention had almost no weight loss after about 3 months.

As can be seen from the above erosion resistance results, it can be seen that the modified sulfur mortar according to the present invention can exhibit a very excellent resistance to erosion against acid and base.

In addition, various modifications, improvements and modifications will be possible to those skilled in the art within the scope of the technical spirit of the claims to be described later in the reformed sulfur reforming mortar for reinforcement and the method of manufacturing the same.

As described above, the reformed sulfur reforming mortar and its manufacturing method according to the present invention can exhibit excellent physical properties in terms of resistance to chemicals and strength even with recovered sulfur and waste materials discharged from factories and the like. Modified sulfur mortar for maintenance reinforcement and a method of manufacturing the same can be provided.

 In addition, the reformed sulfur reforming mortar prepared according to the present invention and a method for manufacturing the modified sulfur mortar using a spray method to the subject such as concrete, metal and wood using a manufacturing method and construction method that can be applied to the modified sulfur thin film with a supersonic mirror. In addition, the recycling of waste can simultaneously meet the benefits of environmental protection and resource recycling.

Claims (7)

A reformed sulfur reforming mortar comprising 30 to 90% by weight of modified sulfur polymer and 5 to 65% by weight of inorganic waste materials. 2. The reformed sulfur reforming mortar of claim 1, further comprising 0.1-1% by weight of an antifoaming agent that suppresses bubble generation by external addition to the reformed sulfur polymer and the inorganic waste material. The method of claim 1, wherein the inorganic waste material is reconstituted sulfur reforming mortar, characterized in that at least one selected from waste fine powder, fly ash, slag, silica powder, silica fume. The reformed reformed sulfur mortar of claim 1, wherein the reformed sulfur polymer is obtained by reacting dicyclopentadiene and an oligomer with sulfur discharged as a by-product from an industrial site. Preparing a slurry by melting 30-90% by weight of the modified sulfur polymer and 5-65% by weight of the inorganic waste material within a temperature range of 120 ° C to 180 ° C; Mixing the slurry with an antifoaming agent that suppresses bubble generation preheated within a temperature range of 120 ° C. to 180 ° C. at 1-10% by weight and 0.1-1% by weight, respectively; Spraying the slurry mixture on the surface of the coating body by using a preheated spray within a temperature range of 120 ° C to 180 ° C; Method for producing a modified sulfur mortar for reinforcing reinforcement, characterized in that consisting of the step of naturally cooling and curing the coating body at room temperature. The method of claim 5, wherein the coating member is preheated by pre-cleaning in a 120 ° C ~ 180 ° C temperature range, characterized in that the repair sulfur reforming mortar manufacturing method. 6. The reformed sulfur reforming mortar for reinforcing reinforcement according to claim 5, wherein the inorganic waste material is at least one selected from waste fine powder, fly ash, slag, silica powder, and silica fume.

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