WO2011071203A1

WO2011071203A1 - Hydrothermal method for making panels for formaldehyde decomposition, and panels made thereby

Info

Publication number: WO2011071203A1
Application number: PCT/KR2009/007447
Authority: WO
Inventors: 이종규; 추용식; 송훈; 임두혁; 강대구
Original assignee: 한국세라믹기술원; (주)에스와이씨
Priority date: 2009-12-11
Filing date: 2009-12-11
Publication date: 2011-06-16
Also published as: KR20110066286A; KR101149066B1

Abstract

The present invention relates to a hydrothermal method for making panels for formaldehyde decomposition, comprising: mixing (a) a base component comprising calcium hydroxide, silica and white cement, (b) a porous inorganic material, and (c) a metal phthalocyanine; press molding the obtained mixture into a predetermined shape of a panel; and carrying out hydrothermal reaction. A panel prepared by the method of the present invention has simultaneously, both adsorption and decomposition activities for volatile organic compounds, and is thus suitable as an interior construction material.

Description

Method for producing hydrothermal synthesized panel for formaldehyde decomposition and panel manufactured therefrom

The present invention relates to an inorganic panel produced by the hydrothermal synthesis method, in particular suitable for use as building interior materials.

Recently, the use of organic materials as building materials is regulated due to human health hazards and fire hazards caused by volatile organic compounds (VOC), and the use of inorganic materials is gradually increasing, and inorganic materials are not only functions of interior materials. It is controlled to express the beneficial functionality to the human body. Such changes in building interior materials have greatly increased the level of consumer's demand due to the widespread public health of organic interior materials caused by broadcasting and other media reports, and accordingly, the functionality of inorganic interior materials has been gradually developed to meet the demand level. to be.

Recently, porous panels having both formaldehyde adsorption and decomposition activity have been manufactured and sold, but they are calcined at high temperature, and are not only energy-saving panels that need to be calcined at 1000 ° C. or higher when manufactured, but are imported from foreign countries. Therefore, it is essential to develop a panel capable of absorbing and decomposing volatile organic compounds such as formaldehyde while being a low energy type low temperature panel.

Accordingly, an object of the present invention is to provide a method for producing an inorganic panel which is produced through an energy-low consumption manufacturing process and has a function of adsorbing and decomposing volatile organic compounds.

The method for producing a hydrothermal composite panel for decomposition of formaldehyde according to the present invention comprises (a) a base component containing slaked lime, silica, and white cement and adjusting the CaO / SiO 2 ratio to 0.6-1.1, (b) a porous inorganic material and (c ) And phthalocyanine metals are mixed under pressure in a predetermined panel and subjected to hydrothermal synthesis at a temperature of 100 ° C to 200 ° C.

Method for producing a hydrothermal panel for decomposition of formaldehyde of the present invention is characterized in that the porous inorganic material is one or a mixture of two or more selected from the group consisting of diatomaceous earth, bentonite, zeolite, metakaolin, ocher and volcanic stone.

In the method for producing a hydrolysis panel for formaldehyde decomposition of the present invention, the porous inorganic material is characterized in that 1 to 30 parts by weight based on 100 parts by weight of the base component.

Method for producing a hydrothermal panel for decomposition of formaldehyde of the present invention is characterized in that the phthalocyanine metal is one or a mixture of two or more selected from the group consisting of phthalocyanine copper, phthalocyanine iron, phthalocyanine nickel.

The phthalocyanine metal is 0.01 to 5 parts by weight based on 100 parts by weight of the base component in the method for producing a formaldehyde decomposition hydrothermal synthesis panel of the present invention.

The method for producing a hydrothermal panel for decomposition of formaldehyde according to the present invention is characterized by further comprising a binder in (a) the base component, (b) the porous inorganic material and (c) the phthalocyanine metal.

In the method for producing a hydrothermal panel for decomposition of formaldehyde of the present invention, the binder is characterized in that the polyvinyl alcohol or water glass.

The hydrothermal synthesis panel for formaldehyde decomposition of the present invention is characterized in that it is produced by the above method.

The panel produced by the method of the present invention is significantly improved formaldehyde adsorption performance compared to the panel that does not contain phthalocyanine metal, as well as extremely low re-release of formaldehyde adsorbed on the panel to formaldehyde decomposes to be used as building interior materials In this case, it provides a very useful effect to provide a comfortable living environment, and provides a panel with excellent formaldehyde decomposition effect while reducing energy consumption compared to the conventional formaldehyde decomposition panel requiring high temperature firing. In addition, the panel produced by the method of the present invention shows excellent efficacy in adsorption and decomposition of volatile organic compounds such as benzene and toluene as well as formaldehyde.

1 is a graph showing the amount of formaldehyde adsorption of a panel in which C / S was changed.

2 is a porous inorganic material, iron source dolomite (G), Figure 3 iron source dolomite (P), Figure 4 is a Chinese dolomite (W), Figure 5 is a Chinese dolomite (P), Figure 6 Pohang bentonite, Figure 7 Hwasun Bentonite, Figure 8 is a racing zeolite, Figure 9 is a graph showing the amount of formaldehyde adsorption according to the content of the porous inorganic material in the panel manufactured using Pohang zeolite.

FIG. 10 is a graph showing the amount of formaldehyde adsorption by concentration of phthalocyanine iron, FIG. 11 is phthalocyanine copper, and FIG. 12 is a panel prepared by adding phthalocyanine nickel.

FIG. 13 is a graph showing toluene adsorption amount according to the addition concentration in a panel prepared by adding phthalocyanine copper, and FIG. 14 is a graph showing the amount of benzene adsorption by addition concentration in a panel prepared by adding phthalocyanine copper.

15 is a graph showing the formaldehyde re-release amount of phthalocyanine iron, Figure 16 phthalocyanine copper, Figure 17 is a phthalocyanine nickel, Figure 18 is a graph showing the formaldehyde re-release amount when 0.3% of each phthalocyanine metal is added.

19 is a graph showing the toluene re-emission amount of phthalocyanine iron, FIG. 20 is a phthalocyanine copper, Figure 21 is a phthalocyanine nickel, Figure 22 is a graph showing the toluene re-emission amount when 0.3% of each phthalocyanine metal is added.

FIG. 23 is a graph showing benzene re-emission amount of phthalocyanine iron, FIG. 24 phthalocyanine copper, and FIG. 25 is phthalocyanine nickel, and FIG. 26 is a graph showing benzene re-emission amount when 0.3% of each phthalocyanine metal is added.

The present invention provides a method for producing a hydrothermal composite panel for decomposition of formaldehyde, comprising: (a) a base component containing slaked lime, silica, and white cement and having a CaO / SiO2 ratio of 0.6-1.1; and (b) a porous inorganic material and ( c) The phthalocyanine metal is mixed, press-molded by a predetermined panel, and subjected to hydrothermal reaction at a temperature of 100 ° C to 200 ° C.

As a base component used in the manufacture of the panel of the present invention, slaked lime, silica, white cement, and the like may be used, and the chemical analysis results of these raw materials are shown in Table 1.

Table 1

Raw material	Chemical Composition (Unit: wt%)
Raw material	SiO ₂	Al ₂ O ₃	Fe ₂ O ₃	CaO	K ₂ O	Na ₂ O	LOI
Slaked lime	2.12	0.77	0.34	69.50	0.11	0.21	26.90
burr	93.80	3.08	1.33	0.06	0.76	0.08	-
Back cement	22.80	6.16	0.26	68.42	0.21	-	0.10

As shown in Table 1, the slaked lime [Ca (OH) ₂ ] has a main component of CaO of 69.50% and a loss on ignition (LOI) of 26.90%. LOI originates from H ₂ O in calcium hydroxide because Ca (OH) ₂ decomposes into CaO and H ₂ O at about 400-500 ° C. The silica is 93.80% SiO ₂ and 3.08% Al ₂ O ₃ . The white cement has a CaO content of 68.42%, a SiO ₂ content of 22.80%, and an Al ₂ O ₃ content of 6.16%.

In the present invention, the CaO / SiO2 ratio of the base component mixture containing slaked lime, silica and white cement is 0.6 to 1.1, preferably 0.65 to 0.8, and most preferably 0.7. If it is out of the above range, the adsorption performance of formaldehyde is lowered in the manufactured panel.

As the porous inorganic material used to manufacture the panel of the present invention, diatomaceous earth, bentonite, zeolite, metakaolin, ocher and volcanic stone are used. Diatomaceous earth was obtained from the 4th diatomaceous earth and diatomaceous earth from China, bentonite from Hwasun and Pohang areas, and zeolite from Gyeongju and Pohang areas. The results are shown in Table 2.

TABLE 2

Raw material		SiO ₂	Al ₂ O ₃	Fe ₂ O ₃	CaO	K ₂ O	Na ₂ O	LOI
Diatomaceous earth	Cheorwon (G)	66.60	15.40	3.64	0.36	2.15	0.78	9.53
	Cheorwon (P)	86.70	6.11	2.07	0.09	1.12	0.17	3.17
	China (W)	88.01	4.20	1.37	0.23	1.85	1.25	0.22
	China (P)	91.15	2.96	1.48	0.25	0.70	0.40	0.24
Bentonite	Hwasun (H)	75.00	14.80	1.51	0.03	4.94	0.23	3.14
Bentonite	Pohang (P)	60.60	16.30	5.24	2.62	1.99	1.71	8.00
Zeolite	Gyeongju (K)	70.30	13.60	1.29	2.51	3.17	1.93	5.76
Zeolite	Pohang (P)	63.20	15.70	3.72	2.54	2.15	2.18	7.64
Volcanic stone		67.10	16.30	4.38	3.08	2.32	3.11	-
ocher		49.50	34.90	5.17	0.28	0.69	-	-

The content of SiO ₂ , the main component of diatomaceous earth, was 66.60 ~ 91.15 wt%, and the ignition loss was widely distributed from 0.22 ~ 9.53 wt%. The SiO ₂ content of bentonite was 75.0% (H) and 60.6% (P), and the Al ₂ O ₃ content was 14.8% (H) and 16.3% (P).

In the manufacture of the panel of the present invention, the porous inorganic material includes 1 to 30 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the base component. If it is less than the lower limit, the formation of nano pores is insufficient, and the adsorption performance of the volatile organic compound is lowered. If the upper limit is exceeded, the physical strength of the panel is lowered.

The phthalocyanine metal used for the panel production of the present invention is one or a mixture of two or more selected from the group consisting of phthalocyanine copper, phthalocyanine iron and phthalocyanine nickel. Among the phthalocyanine metals, phthalocyanine copper has the highest formaldehyde decomposition and adsorption performance. The phthalocyanine metal is used in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 0.5 parts by weight, and most preferably 0.2 to 0.4 parts by weight based on 100 parts by weight of the base component. Below the lower limit, the formaldehyde adsorption capacity enhancement effect is insignificant, the formaldehyde decomposition activity is low, and even if the upper limit is exceeded, there is little effect of increasing the adsorption and decomposition performance relative to the added amount.

The panel production of the present invention may further include a binder such as polyvinyl alcohol, water glass, the amount of the addition is 0 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 1.5 to 100 parts by weight of the base component To 5 parts by weight.

Hereinafter, the present invention will be described in detail by examples and production examples. However, the following examples are merely to illustrate the present invention, but the content of the present invention is not limited thereto.

Experimental Example 1 Formaldehyde Adsorption Amount According to C / S Ratio

First, using only silica, slaked lime (Ca (OH) ₂ ) and white cement as the base component, the CaO / SiO ₂ ratio was changed to 0.5, 0.7, 0.9 and 1.1, wherein each raw material was mixed as shown in Table 3.

TABLE 3

C / S ratio	Base component blending ratio (wt%)
C / S ratio	Slaked lime	burr	Back cement
0.5	30	55	15
0.7 (Ref.)	30	46	24
0.9	30	40	30
1.1	30	34.5	35.5

Each base component of the above compounding was mixed with 10% (mixed water / mixed raw material) of mixed water and then press-molded (Ref). Pressurization was performed for 1 minute by the force of 100kgf / cm ² and then demolded by hydrothermal synthesis. Hydrothermal synthesis was maintained at 180 ° C. for 7 hours.

1 is a graph showing the amount of formaldehyde adsorption of a panel in which C / S was changed. 100 ppm of volatile organic compound (formaldehyde) gas was used. The formaldehyde adsorption characteristics of the panel according to the C / S ratio showed an adsorption performance close to 80% when the C / S ratio was 0.7. However, other C / S ratios showed somewhat lower adsorption characteristics.

Experimental Example 2: Formaldehyde Adsorption According to Type and Content of Porous Inorganic Materials

10% (mixed water / mixed raw material) after mixing the porous inorganic material of Table 2 with 10% to 30% by weight with respect to the base material in the base component blended with the C / S ratio of Table 3 of Experimental Example 1 as 0.7 ) Was mixed with water and then molded under pressure. Pressurization was performed for 1 minute by the force of 100kgf / cm ² and then demolded by hydrothermal synthesis. Hydrothermal synthesis was maintained at 180 ° C. for 7 hours. As a control, the C / S of Experimental Example 1 was 0.7 and was represented as Ref as a panel manufactured without a porous inorganic material.

The use of iron source dolomite (G) as a porous inorganic material in FIG. 2, the use of iron source dolomite (P) in FIG. 3, the use of Chinese dolomite (W) in FIG. 4, the use of Chinese dolomite (P) in FIG. 6 shows that Pohang bentonite is used in FIG. 6, FIG. 7 uses Hwasun bentonite, FIG. 8 uses race zeolite, and FIG. 9 uses Pohang zeolite.

Adsorption capacity of formaldehyde was improved with the use of porous raw materials, and in particular, the rate of formaldehyde adsorption was also increased. In addition, it exhibited excellent adsorption characteristics in Pohang zeolite, iron source diatomaceous earth, and Pohang bentonite. This characteristic is similar to the adsorption characteristic of water, which is assumed to be related to the pore characteristics of the panel. That is, it was determined that the adsorption of formaldehyde increased as the content of nanopores increased.

Experimental Example 3: Formaldehyde Adsorption Rate by Addition of Phthalocyanine Metal

The panel of Experimental Example 2, in which 10 parts by weight of Pohang zeolite was added to 100 parts by weight of the substrate component having a relatively high specific surface area and pore volume and excellent formaldehyde adsorption capacity, was added to 100 parts by weight of the substrate component in the panel manufacturing process using Ref. As the phthalocyanine iron, phthalocyanine copper and phthalocyanine nickel content was added differently, formaldehyde adsorption characteristics were confirmed.

10 shows the amount of formaldehyde adsorption in the panel prepared by adding phthalocyanine iron, phthalocyanine copper in FIG. 11, and phthalocyanine nickel in FIG. 12.

When a small amount of phthalocyanine metal was added, the formaldehyde adsorption capacity increased sharply and the adsorption rate was nearly twice as fast as the panel without the porous raw material as well as the panel without the porous raw material. In addition, as the amount of phthalocyanine added increased, the adsorption capacity was excellent, but the adsorption power of 0.3% and 0.5% added panels did not show a big difference.

On the other hand, the panel prepared by adding phthalocyanine metal confirmed that the adsorption amount of toluene and benzene, which are volatile organic compounds other than formaldehyde, was also increased.In the case of benzene and toluene, like aldehyde, the adsorption capacity and It was confirmed that the adsorption rate rapidly increased. Among them, only the results of confirming the adsorption amount of toluene and benzene on the panel prepared by adding phthalocyanine copper are shown in FIGS. 13 and 14, respectively.

Experimental Example 4: Emission of Volatile Organic Compounds with Addition of Phthalocyanine Metal

In Experimental Example 3, the adsorption experiment of the volatile organic compound was performed for 24 hours, and then the release of the volatile organic compound was confirmed for 12 hours using the specimen. After the adsorption measurement, the specimens were immediately transferred to a clean new container, and the concentration of volatile organic compounds released was checked for 12 hours.

Fig. 15 shows the formaldehyde re-emission amount of phthalocyanine iron, Fig. 16 the phthalocyanine copper, and Fig. 17 the phthalocyanine nickel, and Fig. 18 shows the amount of formaldehyde re-emission when 0.3% of each phthalocyanine metal is added.

19 shows phthalocyanine iron, FIG. 20 shows phthalocyanine copper, FIG. 21 shows the toluene re-emission amount of phthalocyanine nickel, and FIG. 22 shows the toluene re-emission amount when 0.3% of each phthalocyanine metal is added.

FIG. 23 is a phthalocyanine iron, FIG. 24 is a phthalocyanine copper, FIG. 25 is a benzene re-emission amount of phthalocyanine nickel, and FIG. 26 shows a benzene re-emission amount when 0.3% of each phthalocyanine metal is added.

Specimens adsorbed volatile organic compounds were released to some extent over time, but they were insignificant compared to the total adsorption amount. Among them, it was confirmed that the re-release amount of volatile organic compounds of the panel containing phthalocyanine copper was very small and the total adsorption amount was improved by 10% or more compared with Ref.

This means that phthalocyanine copper adsorbs and decomposes volatile organic compounds such as formaldehyde, toluene, benzene and the like. The decomposition of formaldehyde showed the best results in the phthalocyanine copper 0.5% addition panel, and the maximum decomposition rate of formaldehyde was 97%. In addition, the toluene and benzene resolution of the phthalocyanine copper 0.5% addition panel was the best. The decomposition rate of toluene was 98% and that of benzene was 96%.

Claims

(a) Pressurized molding with a panel of predetermined shape by mixing sintered lime, silica and white cement and adjusting the CaO / SiO2 ratio to 0.6-1.1, and (b) porous inorganic material and (c) phthalocyanine metal. And hydrothermal synthesis reaction at a temperature of 100 ° C. to 200 ° C. for producing a hydrothermal synthesis panel for decomposition of formaldehyde.
The method of claim 1, wherein the porous inorganic material is one or two or more mixtures selected from the group consisting of diatomaceous earth, bentonite, zeolite, metakaolin, ocher and volcanic stone.
The method of claim 1 or 2, wherein the porous inorganic material is included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the base component.
The method of claim 1, wherein the phthalocyanine metal is one or a mixture of two or more selected from the group consisting of phthalocyanine copper, phthalocyanine iron, and phthalocyanine nickel.
5. The method of claim 1 or 4, wherein the phthalocyanine metal is contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the base component.
The method of claim 1, further comprising a binder in (a) the base component, (b) the porous inorganic material and (c) the phthalocyanine metal.
The method of claim 6, wherein the binder is polyvinyl alcohol or water glass.
A hydrothermal synthesis panel for decomposition of formaldehyde, characterized in that it is produced by the method of any one of claims 1, 2, 4, 6 and 7.