KR20040101708A - Manufacturing method of vesicant glass for non-combustion adiabatic member of inorganic matter - Google Patents

Abstract

PURPOSE: Provided are production method of foamed glass as inorganic noninflammable and heat insulating materials, and synthetic method of porous and spherical alumina-silica powder as raw materials for foamed glass. CONSTITUTION: The raw materials for the production of foamed glass, alumina-silica powder, are synthesized by the following steps of: mixing Al(OH)3 slurry with sodium silicate and mixing H2SO4 with Al2(SO4)3 (110a, 110b); mixing each solution in an equivalent ratio to form beads (120); spraying a mixed solution with a pressure of 4kg/cm2 through a straw nozzle to get hydro-gel particles(130); aging gel particles at pH10 (140); putting gel particles into H2SO4(pH2) to be particles of pH1 and acid treating for 16hrs with air-bubbling which prevents gel from sedimenting (150); washing the gel with ion-exchanged water until the supernatant of the gel(5%) is above pH7 and has more than 6000ohm·cm of specific resistance (160); thermal-treating washed gel with steam and heating at 80-90deg.C for 18hrs (170); drying gel to be 8% of moisture content (180). The foamed glass is produced by the following steps of: putting prepared alumina-silica powder, raw materials, in a high thermal conductive vessel and placing the vessel in a tunnel or shuttle kiln; firstly elevating the temperature in the kiln to 700-800deg.C to soften alumina-silica particles; secondly elevating the temperature to 1100deg.C over 10-15min and holding at 110-1200deg.C to foam particles homogeneously.

Description

MANUFACTURING METHOD OF VESICANT GLASS FOR NON-COMBUSTION ADIABATIC MEMBER OF INORGANIC MATTER}

The present invention relates to a method for producing an inorganic non-insulating insulation foam glass and a method for producing a raw material used therein, and more specifically, a moisture problem and excessive manufacturing cost due to the capillary phenomenon of the existing inorganic foam insulation material, excessive manufacturing cost, mechanical material itself Method of producing foamed glass for inorganic non-insulating insulation which can improve the problems such as strength reduction, lower firing temperature, reduce processing time, form uniform independent pores and have higher insulation effect and mechanical strength It relates to a method for producing a raw material.

In general, the heat insulating material is mainly used for building exterior materials to block the heat transfer between the temperature of the outside of the building and the temperature inside the building to maintain the temperature inside the building irrespective of the temperature change of the outside.

Among the insulation materials, panels used mainly for building exterior materials include foamed polystyrene foam and polyurethane foam. These insulation materials are mainly vulnerable to fire due to the use of organic materials. It is causing social damage and is emerging as a social problem.

In other words, the most frequent cause of fire accidents, which occur every year, is the combustion of flammable materials that produce toxic gases.The market requirements are also incombustible materials to protect people from such enormous socioeconomic losses and to ensure safety. The use of inorganic insulation is expanding in the market due to the increased use and the revision of government regulations.

Due to these problems, the use of inorganic insulating materials using pressure compresses, glass wool, asbestos, etc. is accelerating. However, when the inorganic insulating materials are used, the thermal insulation performance of the material itself is lower than that of the organic material, and glass or asbestos, etc. Carcinogens due to corrosion floating in the air has emerged as a problem of environmental pollution, and also has a disadvantage in that the cost is expensive due to problems such as replacement time.

In addition, in the case of inorganic insulation materials used for building and exterior materials, flame retardant ratings are regulated to solve the problems caused by the generation of toxic gases in case of fire, and various research results have been proposed, but alternative materials have suggested fundamental solutions. Is not true.

As an alternative to these problems, a lightweight aggregate using foamed glass having heat insulation and processability may be mentioned as a low melting point glass as a heat insulating material that can be used for construction or by mixing waste glass with a blowing agent to form bubbles.

However, currently developed lightweight aggregates have difficulty in producing foam insulation having an apparent specific gravity of 0.2 or less and thermal conductivity of 0.05 kcal / mh ° C. or less as a heat insulating material, and the developed product has a high specific gravity or a capillary phenomenon and Its strength is low and its absorption rate is high due to continuous pores, making it difficult to use as a structure. In particular, the production cost is excessively input such as high-temperature firing process and material loss generated when processing the foamed glass in the form of blocks, which implies a problem of poor practicality.

In order to improve this problem, as a technique for manufacturing a heat insulating material using a conventionally developed foam glass 3 ~ 5k / ㎠ pressure after mixing the raw materials using soda lime glass, calcium carbonate, water glass, clay and alumina Molding by 850 ℃ and firing at 850 ° C. to produce multilayer foamed glass (Korea Patent Publication No. 93-12613), press-molding by press extrusion using soda lime glass powder, calcium hydroxide phosphate compound, clay and alumina, etc. And then fired at 1000 ° C. to manufacture foamed glass having an independent pore structure (Korean Patent Publication No. 97-69916), and 140 mesh powder using SiO 2, Al 2 O 3, B 2 O 3, CaO, MgO, Na 2 O, and C. It is made into a mold and fired at 850 ℃ ~ 900 ℃ to prepare a foamed glass of homogeneous waste hole tissue (Korean Patent Publication No. 99-76196) and the like.

However, such a technique in manufacturing foamed glass, in order to exhibit excellent characteristics, the interior pores should be a closed cell (pore cell), and also to be formed uniformly to achieve a uniform mixing state of the blowing agent and the glass material It should be maintained, and it should be possible to make small adjustments, but it is not easy for the existing manufacturing method.

In addition, the existing technologies have a problem in that the manufacturing cost is excessively input by firing for a long time at a high temperature temperature, and the foamed glass produced is vulnerable to physical shock, which makes it difficult to commercialize. In addition, there is no economic feasibility due to the lack of technology scale for mass production. To date, there are few practical products using foam glass in Korea, and some companies manufacture and sell them depending on imported lightweight aggregate. It is limited.

Therefore, the contents of the research for the development of foam glass products are excellent in mechanical strength and thermal properties of the material itself, and it is necessary to study a manufacturing method that can maintain a uniform closed cell inside the foam glass and can produce at low cost. It is the current situation.

The present invention is to overcome the above-mentioned conventional problems, an object of the present invention is to form a primary particle of 3 ~ 4 Nanometer size using nanotechnology, 0.5 ~ 20 Nanometer size by the growth and self-assembly of primary particles It is in the manufacture of porous spherical particles having pores.

Another object of the present invention is to prepare an ultra-low temperature specific gravity insulation material using the physical and chemical properties of the functional groups present in the pores of 0.5 ~ 20 Nanometer size, the capillary phenomenon of the existing inorganic insulation material It is to improve the thermal conduction problem.

Another object of the present invention is to provide a manufacturing method that can be put to practical use by lowering the firing temperature and reducing the processing time to realize a low manufacturing cost, and to ensure excellent quality and mechanical strength as a heat insulating material with uniform independent pores.

One feature of the present invention for achieving the above object is a mixture of aluminum hydroxide [Al (OH) ₃] slurry and sodium silicate, and mixing sulfuric acid and aluminum sulfate; The mixture is fed and stirred at a reaction equivalent ratio to produce beads; Spraying through a straw nozzle to form a kernel; Aged to maintain the grain at pH 10; The grains were added to sulfuric acid solution having a pH of 2 to add sulfuric acid to pH 1.0, followed by acid treatment for 16 hours; Washing with ion-exchanged water at a flow rate such that the gel does not settle until the pH of the gel 5% supernatant is at least 7.0 and the resistivity is at least 6000 Ωcm; Heat-treating the gel with steam to heat it to about 80-90 ° C. for about 18 hours; And it is to provide a method for producing a raw material used in the manufacture of the foamed glass for inorganic incombustible insulation comprising a step of drying the gel to a water content of about 8%.

In the grain forming step, the injection pressure of the straw assembly nozzle is 4 kg / cm 3, so that the polymerized liquid drops freely to form a spherical hydrogel, and the acid treatment step supplies air to prevent sedimentation of the gel. It is preferable to perform the air bubble treatment.

In another aspect, the raw material used to manufacture the foamed glass for the inorganic incombustible insulating material prepared by the above method is put into a container having high thermal conductivity, and the temperature is elevated to 700 to 800 ° C. by using a tunnel kiln or a shuttle kiln for a predetermined time. The silica granules can be softened, and the temperature is secondly raised to 1100 ° C. over 10 to 15 minutes and then maintained at a temperature of 1100 to 1200 ° C. for several minutes so that the granules can be foamed.

Another feature of the present invention is to mix with an inorganic binder such as alumina silica granules and water glass into a mold and to form a foamed glass block for insulating material in the form of a block through the firing process.

BRIEF DESCRIPTION OF THE DRAWINGS It is process drawing which shows the manufacturing method of the raw material used for manufacture of foamed glass for inorganic non-insulating insulation.

2 is a view showing a bead state of the foamed glass for inorganic incombustible insulation.

3 is an enlarged view showing the fracture surface structure of the foam glass beads by 100 times.

* Description of the main parts of the drawings *

110a, 110b ... mixing step 120 ... stirring step

130 ... granulation step 140 ... ripening step

150 ... Acid treatment step 160 ... Cleaning step

170 ... heating step 180 ... drying step

Briefly explaining the main points of the technical idea of the present invention, starting materials are formed in solution to form 3 to 4 nanoscale primary particles, and the primary particles are grown and self-assembled for use in each industrial field. It is made of a raw material of heat insulating material having suitable mechanical and thermal properties.

In addition, by using the physicochemical properties of functional groups present on the inside and outside of the surface of the starting material having nanopores, a foundation for controlling foaming magnification, mechanical properties, pore structure, etc. by specific temperature control is provided. It is.

According to the present invention, a foam in a vacuum state having closed pores is formed using a mechanism of generating a gaseous substance by condensation polymerization in a specific region by using physicochemical properties of silanol groups present on and inside of silica having nanopores. The technical content for forming and providing a non-combustible heat insulating material having heat insulating and heat insulating properties even in an ultra high temperature state using this material is as follows.

First, Si (OH) ₄ is produced by peptization of sodium silicate to produce primary particles having a size of 2 to 20 Nanometer, and the resulting primary particles are aggregated into a three-dimensional network structure to about 0.5-30 nm. A porous silica having a pore size of is synthesized.

Second, the foamed inorganic insulation material for low specific gravity non-combustible insulation using gas components generated by condensation polymerization at a specific temperature is developed by using the thermal properties of silanol groups on the porous surface and inside.

Third, by using inorganic insulation material with close pores close to the vacuum state developed, it is possible to replace the heat-insulating material that generates toxic gases during combustion and combustion such as polystylene, polyurethane, etc. It is.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.

Referring to Figure 1, a process diagram showing a method for producing a raw material used in the production of foamed glass for inorganic incombustible insulation according to the present invention is shown.

First, the production of the foamed glass for inorganic incombustible insulation according to the present invention is first mixed with aluminum hydroxide [Al (OH) ₃] slurry and sodium silicate in the first step (110a, 110b), and separately from sulfuric acid and aluminum sulfate Prepare the solution.

The mixed solution thus prepared is filled in the respective raw material tanks and then supplied in a reaction equivalent ratio to undergo a stirring step 120 to generate beads.

When the beads are generated through stirring as described above, in the next step 130, the beads are sprayed to be formed into a grain through the straw nozzle. At this time, the injection pressure of the straw assembly nozzle was 4 kg / cm 3. The polymerized droplets are free-falling to form spherical hydrogels.

Thereafter, the granules formed into spherical hydrogels are maintained at about pH 10 while undergoing the aging step 140.

Since the gel produced through the aging step 140 is very weak to external impact, the sulfuric acid solution having a pH of about 2 is transferred to a tank containing sulfuric acid solution for strength, so that sulfuric acid does not change from about 1.0 at pH 1.0. The acid treatment step 150 is subjected to an acid atmosphere for 16 hours. At this time, in order to prevent the sedimentation of the gel is supplied to the air inlet air bubble.

After the acid treatment, the gel is subjected to the washing step 160 with ion-exchanged water until the pH of the gel 5% supernatant at a flow rate such that the gel does not settle and the specific resistance is more than 6000Ωcm.

As such, the gel is heat-treated with steam after the washing step 160 and is subjected to the heating step 170 for about 18 hours at about 80 to 90 ° C., and after the heat treatment is completed, the gel is dried to have a water content of about 8%. 180).

Through this process, spherical porous alumina silica granules, which are raw materials for non-combustible insulation, can be obtained.

The general characteristics of the porous alumina silica granules, which are the raw materials of the non-combustible heat insulating material thus prepared, have the following performance and specifications, and these characteristics can be adjusted according to the treatment conditions such as the composition, temperature, and time of the components introduced during the manufacturing process.

1) Specific surface area: 550㎡ / g

2) Pore diameter: 3nm

3) Pore volume: 0.4mL / g

4) Bulk density: 0.7g / mL

5) Adsorption capacity: RH 40-23, RH 80-36

6) Crash strength: 20kg / ㎠

7) Al2O3 content: 10-15%

When the spherical alumina silica granule raw material prepared as described above is put into a container having excellent thermal conductivity and fired using a tunnel kiln or shuttle kiln, the shaft is formed at a specific temperature due to the thermal properties of silanol groups present on the surface and inside of the porous alumina silica. By the gas component generated by the polymerization can be produced foam granules for low specific gravity non-combustible insulation.

Such a manufacturing method increases the temperature to the first 700 ~ 800 ℃ for a certain time to soften the alumina silica grains, and after raising the temperature for 10 to 15 minutes to the second 1100 ℃ after 1100 ~ 1200 ℃ temperature moisture To keep the granules evenly foamed.

Then, by adjusting the slow cooling time so that the surface of the granule is homogeneous and maintains its strength, the micropores of the three-dimensional network structure are formed therein, and the granular surface is hardened, so that the granules become foamed glass beads for thermal insulation having closed pores. .

The properties of the foam glass beads for insulation can be adjusted in size, strength and density to suit the end use.

This is possible by controlling the composition of the raw materials and the firing process.

Another manufacturing method is the same as the foam glass beads manufacturing method, but mixed with an inorganic binder such as porous alumina silica granules and water glass, and then put in a container (form) having good thermal conductivity, and proceeds to the baking process of the contents for block-shaped insulation Foamed glass blocks can be manufactured.

When comparing the heat insulating material according to the present invention manufactured in such a manner and the existing heat insulating material, as follows.

Comparison of insulation properties for existing insulation panels Item Organic Inorganic system EPS foam Urethane foam Rock wool Glass wool The present invention importance 0.015-0.04 0.025-0.05 0.05-0.35 0.01-0.1 0.15-0.85 Thermal Conductivity (kcal / mh ℃) 0.022-0.03 0.022-0.025 0.024-0.047 0.03-0.055 0.05 or less Vapor permeability (g / ㎡.min) Very low lowness 100 or more 100 or more Very low Capillary phenomenon none none slightly Slightly severe none Decomposition over temperature (℃) 190 weakness Heat resistance Heat resistance Heat resistance Hazard Hazardous Gas Generation Hazardous Gas Generation Contains carcinogens Harmless Harmless Operating temperature (℃) 80 100 600 350 1,000 or more

As described above, it can be seen that the heat insulating material according to the present invention has a higher specific gravity, lower thermal conductivity, and no vapor permeability than the existing heat insulating material. In addition, it can be seen that there is no capillary phenomenon, which is the most problematic in the existing heat insulating material, and also no environmental pollutants such as harmful gases or carcinogens are emitted.

As described above, the present invention is made of a foamed glass prepared by the method for producing a non-combustible insulation foam glass as described above made of an entity having a fine pores therein, as well as thermal insulation, as a mineral of fire safety and harmful by fire non-combustible It is harmless to the human body due to no generation of gas. Especially, it can be manufactured with independent granules, so it is easy to apply to industrial fields requiring heat insulation, insulation, cold storage, and corrosion resistance.

There is no cause of environmental destruction and human damage such as toxic gas, carcinogen, and non-recyclable as in the existing heat insulating material, as well as preservation and resource saving of depleted fossil fuel.

What has been described above is only one embodiment according to the present invention, and the present invention is not limited to the above-described embodiment, and the present invention belongs without departing from the gist of the present invention as claimed in the following claims. Anyone skilled in the art will have the technical spirit of the present invention to the extent that various modifications can be made.

Claims (5)

Mixing aluminum hydroxide [Al (OH) ₃] slurry with sodium silicate and mixing sulfuric acid and aluminum sulfate (110a and 110b), respectively; The mixture is fed and stirred (120) in a reaction equivalence ratio to produce beads; Spraying through a straw nozzle to form a kernel (130); The grain is aged to be maintained at pH 10 (140); The grains are added to sulfuric acid solution having a pH of 2 to add sulfuric acid to pH 1.0, followed by acid treatment for 16 hours (150); Washing with ion-exchanged water (160) until the gel has a pH of at least 7.0 and a resistivity of at least 6000 Ωcm at a flow rate such that the gel does not settle; Heat-treating the gel with steam to heat it to about 80 to 90 ° C. for about 18 hours (170); And Method for producing a raw material used in the production of foam glass for inorganic incombustible insulation comprising the step of drying the gel to a water content of about 8%. [Claim 2] The foam glass for inorganic insulators according to claim 1, wherein the injection pressure of the straw assembly nozzle in the grain forming step 130 is 4 kg / cm < 3 > to form spherical hydrogels while freely dropping the polymerized droplets. Process for the preparation of raw materials used in the manufacture of The method for producing a raw material according to claim 1, wherein the acid treatment step (150) is performed to supply air to prevent the sedimentation of the gel and to perform air bubble treatment. The raw material used to manufacture the foamed glass for inorganic non-combustible insulation prepared by the method of any one of claims 1 to 3 is put in a container with high thermal conductivity to the first 700 ~ 800 ℃ by using a tunnel kiln or shuttle kiln Mineral nonflammable to raise the temperature for a certain time to soften the alumina silica granules, and to raise the temperature for 10-15 minutes in the second time to 1100 ℃ and then maintain the temperature at 1100 ~ 1200 ℃ for a few minutes. Method of manufacturing foamed glass for insulation. A method of molding a foamed glass block for heat insulating material in the form of a block by mixing with an inorganic binder such as alumina silica granules and water glass and putting it in a formwork.