TWI414356B - A dsorbable catalyzer making up of cuprous oxide and zeolite - Google Patents

Abstract

The present invention provides an adsorbable catalyzer making up of cuprous oxide and zeolite and preparing method thereof. The adsorbable catalyzer contains a zeolite material and a plurality of cuprous oxide particles integrated and scattered in the zeolite material. The zeolite material is making up of silica and sodium silico-aluminates with specific ratio. The zeolite material can be used to adsorb and decompose the common pollutants in the air for its features of having a plurality of tiny holes and high specific surface area. And the cuprous oxide particles can affect the cell membrane of bacteria for the features of small particle size and high specific surface area. The adsorbable catalyzer of this invention can adsorb pollutants in the air as well as exhibit sterilizing effect, and has excellent capability as an air cleaner and a disinfectant.

Description

Method for producing adsorption catalyst combining copper oxide and zeolite

The invention relates to a method for producing an adsorption catalyst, in particular to a method for producing an adsorption catalyst combining copper oxide and zeolite.

In recent years, with the development of industrial and commercial development and social structure, people's lifestyles and living environment have also undergone considerable changes. According to the study, people stayed in the indoor environment for more than 80% of the time. The types of modern buildings and air conditioners, the various decorative materials used, and various indoor activities have led to many new sources of indoor air pollution. Some air-conditioning systems may become hotbeds of pollution sources and may spread bioaerosols. In addition, the type of indoor activity may also cause pollution. For example, smoking and indoor fume can cause accumulation of various chemicals and respirable particulates. All of these species may have different levels of impact on human health in life, so people are beginning to pay attention to indoor air quality.

At present, many reports indicate that biogas glue, which is commonly found in the general atmosphere and indoor environment, is one of the main sources of problems such as allergic reactions and infectious diseases in the human body. Therefore, the problem of indoor air quality caused by biogas glue is increasingly Received attention. According to the National Institute for Occupational Safety and Health (NIOSH) survey of indoor air quality problems, the main sources of indoor pollutants are outside air, indoor personnel, air conditioning systems, building materials, business equipment and supplies. And six sources of indoor organic matter, among which bacteria and fungi are the most common and common sources of pollution in indoor environments, and are the mainstay of biogas glue. body. In a multi-person activity or in a poorly ventilated environment, it is easy to cause an increase in biogas glue in the air (Li, CS, and Kuo, YM, "Airborne Characterization of Fungi Indoors and Outdoors," Journal of Aerosol Science, 23(1) , 667-670, 1992), although it does not necessarily cause direct and obvious damage to health, but if the concentration of bacteria in the air is high, it can be reasonably assumed that people in the environment are relatively more likely to be infected.

In various indoor environments, medical institutions have relatively high density of viruses and bacteria. In addition to posing a serious threat to patients with weak resistance, the chances of infection of generally healthy people are relatively increased (Lin, WH). , Chen, YH, and Pai, JY, "Bioaerosol Characteristics in a Hospital," The Chung Shan Medical Journal, 15(1), 97-108, 2004). In addition, due to the demand for its operating characteristics, it is necessary to have higher standards for indoor environment and air quality. Although activated carbon and other adsorption catalysts used in air cleaners are available on the market, and can achieve the desired effect of improving indoor air quality, in order to provide better air improvement effects and a safer and healthier living environment, There is a need to continuously develop adsorption catalysts with better adsorption and sterilization performance to further enhance air purification efficiency, thereby reducing the presence of airborne pollutants, bacteria or microorganisms that are harmful to human health and providing a better life. Environmental quality.

Accordingly, it is an object of the present invention to provide a method for producing an adsorption catalyst comprising a combination of cuprous oxide and zeolite which reduces the concentration of biogas in the air to achieve a sterilization effect.

Thus, the method for producing an adsorption catalyst of cuprous oxide and zeolite according to the present invention comprises the steps of: (i) uniformly mixing a predetermined proportion of ceria with sodium strontium aluminate to form a zeolite component; (ii) a gelling agent is added to the zeolite component and mixed to form a micro-viscous colloidal mixture; (iii) a predetermined amount of cuprous oxide particle component is added to the colloidal mixture and mixed with the colloidal mixture , 揉 and to a uniform form of a colloidal adsorbent premix; (iv) forming the adsorbent premix into a type of adsorbent catalyst preform selected from the group consisting of a predetermined molding method : strips, flakes, powders, spheres and granules; (v) increasing the temperature to 100 ° C ~ 150 ° C by gradually increasing the temperature, and introducing air or nitrogen to the steps under these conditions (iv) drying the prepared adsorption catalyst preform; and (vi) calcining the adsorbent catalyst preform dried by the step (v) at a temperature of from 105 ° C to 450 ° C. After ~3 hours of calcination time, an adsorption catalyst combining cuprous oxide with zeolite can be obtained.

The invention relates to a method for preparing an adsorption catalyst of cuprous oxide and zeolite, which has the beneficial effects that: by adjusting the mixing ratio of cerium oxide and sodium strontium aluminate, the type of zeolite in the obtained adsorption catalyst can be directly changed. In addition, after mixing the cerium oxide and the strontium aluminate, the cuprous oxide particles are added and calcined to produce an adsorption catalyst which is structurally stable and has a predetermined content of cuprous oxide particles. The manufacturing method of the invention can facilitate oxygen The cuprous particles are combined with the zeolite substrate to produce an adsorption catalyst having both adsorption and sterilization performance.

The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments.

Referring to Figure 1, a preferred embodiment of the present invention incorporating a cuprous oxide and zeolite adsorption catalyst 2 comprises a zeolite substrate 21 and a plurality of cuprous oxide particles 22 bonded to and dispersed on the zeolite substrate 21.

The zeolite substrate 21 is made by mixing a predetermined ratio of cerium oxide with sodium strontium aluminate. Among them, the type of the zeolite substrate 21 should not be limited, and a specific type of zeolite can be produced according to the application requirements. therefore. The zeolite substrate 21 may be made of a zeolite selected from the group consisting of zeolite A, zeolite L, zeolite M, zeolite MCM, zeolite X, zeolite Y, zeolite ZSM, beta. Zeolite, mordenite, ferrierite and potassium zeolite. In order to obtain a preferred adsorption effect, the zeolite substrate 21 is preferably a Y-type zeolite.

The cuprous oxide particles 22 are substantially bonded and interspersed within the interior and surface of the zeolite substrate 21. And it can react with the biogas gel adsorbed on the pores or surfaces inside the zeolite substrate 22 to achieve the sterilization and sterilization effect (Ren, G., Hu, D., Cheng, E., Vargas-Reus, M. Reip, P., and Allaker, R., "Characterisation of copper oxide nanoparticles for antimicrobial applications," International Journal of Antimicrobial Agents, 2009).

The appearance of the adsorption catalyst 2 should not be limited, and can be applied according to the application and design. According to the demand, different types of adsorption catalysts can be produced by different molding machines. Therefore, the adsorption catalyst can be made into a type selected from the group consisting of strips, flakes, powders, spheres and pellets. . The adsorption catalyst is mainly prepared by thoroughly mixing a zeolite component forming the zeolite substrate 21 with a predetermined amount of cuprous oxide particle component, and then molding and calcining. Wherein the zeolite component substantially comprises 65 wt% ceria and 35 wt% sodium strontium aluminate.

Referring to Fig. 2, the adsorption catalyst of the present invention in combination with cuprous oxide and zeolite can be obtained by the following manufacturing method. The preferred embodiment of the manufacturing method comprises the following steps: In step 101, a predetermined ratio of cerium oxide and sodium cerium aluminate are uniformly mixed to form a zeolite component. By varying the ratio of cerium oxide to sodium strontium aluminate, zeolite substrates with different bismuth to aluminum ratios can be made and affect the stability and selectivity of the zeolite. In the present embodiment, the weight ratio of cerium oxide to sodium cerium aluminate in the zeolite component was 65:35. In this ratio, a Y-type zeolite having a strong adsorption selectivity to non-polar organic molecules can be produced.

In step 102, a gelling agent is added to the zeolite component and mixed to form a colloidal mixture having a slight viscosity. The components of the zeolite component are uniformly mixed into a gel by a gelling agent. Preferably, the gelling agent may use a material selected from the group consisting of sodium hydroxide, sulfuric acid, hydrochloric acid and water. In the present embodiment, sodium hydroxide having a concentration of 0.75 N was used as a gelling agent, and it was slowly dropped into the uniformly mixed zeolite component until a colloidal dough was formed.

Step 103 is to add a predetermined amount of cuprous oxide to the colloidal mixture. The particle component is mixed with the colloidal mixture and kneaded to homogeneity to form a colloidal adsorbent premix. Wherein, according to the subsequent experimental data, when the weight ratio of the cuprous oxide particle component of the adsorbent premix to the zeolite component is 1:99 to 50:50, a predetermined sterilization effect can be obtained, and When the weight ratio of the mixture is 3:97~50:50, the sterilization effect is significantly improved. Further, more preferably, when the weight ratio of the cuprous oxide particle component to the zeolite component is from 3:97 to 5:95, an excellent amount of the cuprous oxide particles can achieve an excellent sterilization effect. Therefore, under the principle of taking into account the cost of raw materials and the performance of sterilization, this is the optimal range of dosage ratio.

In step 104, the adsorbent premix is formed into a type of adsorption catalyst preform selected from the group consisting of strips, flakes, powders, spheres and granules by a predetermined molding method. In the present embodiment, the adsorbent premix is prepared into a strip-shaped adsorbent catalyst preform by a hydraulic press.

In step 105, the temperature is raised to 100 ° C to 150 ° C in a manner of gradually increasing the temperature, and air or nitrogen is introduced to dry the adsorption catalyst preform obtained in the step 104 under the conditions. The drying time of the adsorption catalyst preform can be adjusted according to the level of the final drying temperature. In the present embodiment, the adsorption catalyst preform is dried for 8 hours after the temperature is raised to 105 °C.

Step 106: calcining the adsorption catalyst preform dried in step 105 at a temperature of 105 ° C to 450 ° C. Since the present embodiment is dried at a temperature of 105 ° C, it is preferred to exceed the temperature of 105 ° C. After calcination, after 1 to 3 hours of calcination time, combined with cuprous oxide and boiling The zeolite adsorption catalyst, the zeolite in the obtained adsorption catalyst is preferably a Y-type zeolite. If the calcination temperature is too low, the sintering phenomenon is less likely to occur, resulting in a lower mechanical strength of the adsorbent catalyst produced, but if the calcination temperature is too high, the cuprous oxide is easily oxidized to copper oxide.

Hereinafter, the production method of the cuprous oxide/zeolite adsorption catalyst of different mixing ratios and the ability to remove microorganisms and bacteria in the air will be further described by the following specific examples.

<Specific Example 1 - Preparation of Adsorption Catalyst Combining Cuprous Oxide with Zeolite>

Hereinafter, the mixed weight ratio of the cuprous oxide particle component to the zeolite component is represented by A/B, for example, the 5/95 adsorption catalyst means 5 parts by weight of the cuprous oxide particle component and 95 parts by weight of the zeolite group. The Cu ₂ O/Zeolite adsorption catalyst (hereinafter referred to as CZ adsorption catalyst) prepared by mixing is mixed.

(1) Preparation of CZ adsorption catalyst of 1/99: 35 g of sodium strontium aluminate and 65 g of cerium oxide were mixed to form a zeolite component, and then 0.75 N of sodium hydroxide was slowly dropped. In the zeolite component, until a micro-viscous colloidal mixture is formed, 1.01 g of the cuprous oxide particle component is added, and after mixing and kneading to form a colloidal adsorbent premix, the premixing is performed. The product is placed in a hydraulic forming machine to prepare a plurality of strip-shaped adsorption catalyst preforms, and then the adsorption catalyst preforms are placed in an oven, and the temperature of the oven is gradually raised to 105 ° C, and air is introduced. The drying treatment was carried out for 8 hours, and finally, calcination was carried out at a high temperature exceeding 105 ° C to obtain a CZ adsorption catalyst of 1/99, and the code was designated as CZ01.

(2) Preparation of CZ adsorption catalyst of 3/97: as in the method described in (1), the amount of sodium strontium aluminate and cerium oxide is the same, except that the added cuprous oxide is added. The particle composition was changed to 3.09 g, and the remaining operation modes and conditions were maintained. According to this, a 3/97 CZ adsorption catalyst was obtained, and its code was designated as CZ03.

(3) Preparation of 5/95 CZ adsorption catalyst: In the same manner as in (1), the amount of sodium strontium aluminate and cerium oxide is the same, except that the added cuprous oxide particle component is changed to 5.26 g. The remaining operation modes and conditions remain unchanged. According to this, a 5/95 CZ adsorption catalyst is prepared and its code number is CZ05.

(4) Preparation of 30/70 CZ adsorption catalyst: Same as (1), the amount of sodium strontium aluminate and cerium oxide is the same, except that the added cuprous oxide particle component is changed to 42.86 grams. The rest of the operation methods and conditions remain unchanged. According to this, a 30/70 CZ adsorption catalyst is obtained, and its code is designated as CZ30.

(5) Preparation of 50/50 CZ adsorption catalyst: Same as (1), the amount of sodium strontium aluminate and cerium oxide is the same, except that the added cuprous oxide particle component is changed to 100 gram. The remaining operation modes and conditions remain unchanged. According to this, a 50/50 CZ adsorption catalyst is prepared and its code number is CZ50.

(6) Preparation of 40/60 CZ adsorption catalyst: Same as (1), the amount of sodium strontium aluminate and cerium oxide is the same, except that the added cuprous oxide particle component is changed to 66.67 gram. The rest of the operation methods and conditions remain unchanged. According to this, a 40/60 CZ adsorption catalyst is prepared and its code number is CZ40.

<Specific Example 2 - Analysis of physicochemical properties of CZ adsorption catalyst>

(1) Crystal phase analysis: According to the method described in (1) of <Specific Example 1>, the calcination temperature was set to 105 ° C, 200 ° C and 450 ° C, respectively, to prepare CZ50 adsorption treatments with different calcination temperatures. Catalyst, in addition, the calcination temperature was set to 105 ° C and 450 ° C, respectively, to prepare the CZ40 adsorption catalyst treated by the first two calcination temperatures, respectively, obtained by X-ray diffractometer for different calcination temperatures. The CZ50 and CZ40 adsorption catalysts were analyzed by crystal phase and compared with the standard spectra.

Fig. 3 and Fig. 4 show the results of crystal phase analysis of CZ50 and CZ40, respectively. When the main diffraction peak appears at 2θ=36.35-36.55 and 42.3, it is the main peak of cuprous oxide, and the main peak of Y type zeolite at 2θ=20-30. It is shown that the adsorption catalyst prepared by the present invention does contain cuprous oxide and zeolite, and the crystal phase diagram of the adsorption catalyst prepared at a calcination temperature of 450 ° C shows that in addition to the main peak appearing at the above position The main peak of copper oxide appears at 2 θ=35.5-38.7, and it is presumed that when the calcination temperature is raised, part of cuprous oxide will react with oxygen in the air to oxidize to copper oxide, so that the concentration of cuprous oxide is relatively The reduction may affect the sterilization efficiency of the adsorption catalyst. Therefore, the calcination temperature should not be too high, and it is best not to exceed 450 °C.

(2) Scanning electron microscope (SEM) observation: Image analysis of CZ40 and CZ50 adsorption catalysts prepared by <Specific Example 1> by SEM, and the results are shown in Fig. 5 (a), (b), and (c). (d), where (a) and (b) are observations of CZ40 at different magnifications, and (c) and (d) are observations of CZ50 at different magnifications, based on the obtained images. As a result, it can be seen that the granular cuprous oxide particles are respectively bonded to the zeolite substrate, and a part of the cuprous oxide particles are coated with a substance, which is presumed to be added with cerium oxide and sodium strontium aluminate in the manufacturing process. Caused.

The results of the analysis of the physical and chemical properties of (1) and (2) show that the production method of the present invention can produce an adsorption catalyst combining copper oxide with zeolite.

<Specific Example 3 - Biogas gel sampling analysis>

Referring to Figure 6, a sampling system is provided, the sampling system including an Anderson 6-stage Andersen microbial particle sizing (abbreviated as AMS 6 Sstage, pore size: 1.2~0.25 mm, number of holes: 400, cut-off particle size: 7.0-0.65 μm, sampling flow rate: 28.3 L/min) An exhaust pump 4 and a straight column 5 respectively connected to the gas outlet end portion 31 and the inlet end portion 32 of the sampler 3 are provided.

The adsorption catalysts 2 of CZ01, CZ03, CZ05, CZ30, and CZ50 prepared in <Specific Example 1> were respectively filled in the straight column 5 of the sampling system, the filling amount was 30 g, respectively, and the medium containing the medium was cultured. The dish 6 is placed in the sampler 3 of the sampling system for sampling. Among them, there are two kinds of culture medium for sampling, which are TSA (Tryptic soy agar) medium for collecting bacterial biogas glue, and MEA (Malt extract agar) medium for collecting fungal biogas gel. Sampling was performed to separately detect the biogas gel concentration of bacteria and fungi at the site. The detection method is carried out according to the detection method of total bacteria and total fungi in indoor air announced by NIEA E301.11C and 0970102006A NIEA E401.11C of China Environmental Protection Department No. 097010.

The sampling location is the office on the 8th floor of the Huan'an Museum of Yunlin University of Science and Technology. After the prepared adsorption catalyst 2 is filled into the sampling system, the sampling system is placed at a height of about 120 to 150 cm from the ground and recorded. The collection time, the volume of the air sample, the ambient temperature and humidity of the sampling site. Next, the culture dish 6 containing the medium is placed in the sampler 3, and an appropriate amount of air volume is set, and the biogas particles are collected on the medium in an impact manner, and the suction time should not exceed 10 minutes, so as to avoid microbial dehydration. Can not be cultivated, the sampling needs to be repeated twice and averaged, and Send to laboratory culture within 24 hours after sampling.

After sampling, the culture dish containing the TSA medium was cultured in an incubator at 30±1° C. for 48±2 hours, and the culture dish containing the MEA medium was placed in an incubator at 25±1° C. for 4±1 days. After the cultivation, the number of colonies on the two media was counted separately, and the biogas gel concentration was calculated by the following formula:

In addition, the sampling system is also used to collect indoor air and culture and count colonies in a culture dish containing TSA medium and MEA medium, respectively, without filling the adsorption catalyst prepared by the present invention, to calculate the indoor background of the sampling place. Biogas gel concentration.

Finally, the biogas gel concentration measured by the CZ01, CZ03, CZ05, CZ30, and CZ50 adsorption catalysts 2 is divided by the biogas gel concentration of the indoor background (ie, the case where the adsorption catalyst is not filled), and then 1 After deducting and multiplying by 100%, the sterilization rate of the aforementioned adsorption catalyst 2 can be obtained.

(result)

As shown in Fig. 7, after the 30 g of CZ01, CZ03, CZ05, CZ30, and CZ50 adsorption catalysts were filled in the sampling system, the biogas gel concentration data of the TSA and MEA medium obtained by the detection were further calculated. Bacterial rate value. According to the test results, CZ01 has 60% of the fungi, and when the weight ratio of the cuprous oxide component to the zeolite component is 3:97, that is, the CZ03 sterilization rate is increased to more than 90%, and CZ03, The sterilization rates of CZ05 and CZ30 are all maintained above 90%. When the amount of cuprous oxide is increased to CZ50, the sterilization rate is even higher than 95%. The effect of the bacteria, according to the invention, the adsorption catalyst of the cuprous oxide and the zeolite has excellent sterilization performance, and the sterilization effect can be significantly improved by using only a small amount of cuprous oxide, indicating that the adsorption catalyst of the invention has Can be applied to the practical benefits of sterilization-related products.

In summary, the present invention, in combination with the method for producing an adsorption catalyst of cuprous oxide and zeolite, can attain the following efficacies and advantages, and thus achieve the object of the present invention:

1. The experimental results of <Specific Example 3> show that the sampling system filled with the adsorption catalyst of the present invention combined with cuprous oxide and zeolite has excellent sterilization effect, that is, collected by TSA medium and MEA medium. The biogas gel concentration of the sample is significantly decreased, indicating that the adsorption catalyst of the present invention can effectively remove bacteria and fungi in the biogas gel in the air, and exerts the effect of sterilization, so it has developed into a general indoor or medical institution. The application value of the sterilization-related products can also be further developed into the adsorption materials used in the air cleaning equipment.

2. The physicochemical property analysis result of <Specific Example 2> shows that the manufacturing method of the present invention can produce a binding contact of cuprous oxide and zeolite by mixing a predetermined ratio of ceria, strontium aluminate and cuprous oxide particles. The medium has the effect of adsorbing and removing air pollutants and bacteria in the air by the adsorption characteristics of the porous zeolite substrate and the bactericidal effect of the cuprous oxide particles. Therefore, the cuprous oxide particles can be easily facilitated by the manufacturing method of the present invention. It is combined with a zeolite substrate to produce an adsorption catalyst having both adsorption and sterilization performance.

However, the above is only the preferred embodiment of the present invention, and the scope of the present invention cannot be limited thereto, that is, the patent application according to the present invention The scope of the invention and the equivalent equivalents and modifications of the invention are still within the scope of the invention.

2‧‧‧Adsorption catalyst

21‧‧‧ Zeolite substrate

22‧‧‧ cuprous oxide particles

3‧‧‧sampler

31‧‧‧Exhaust end

32‧‧‧Intake end

4‧‧‧Exhaust pump

5‧‧‧ straight column

6‧‧‧ Petri dishes

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a partial cross-sectional view showing a state in which a plurality of cuprous oxide particles are bonded to a zeolite substrate of a preferred embodiment of the adsorption catalyst of the present invention; and Figure 2 is a view showing the combination of cuprous oxide and zeolite in the present invention. A flow chart of a preferred embodiment of the method for producing an adsorption catalyst; and FIG. 3 is a map obtained by measuring an adsorption catalyst (CZ50 adsorption catalyst) prepared by different X-ray diffractometers at different calcination temperatures; Figure 4 is a map obtained by measuring the adsorption catalyst (CZ40 adsorption catalyst) prepared by different X-ray diffractometers at different calcination temperatures; Figure 5 is a scanning electron microscope photograph showing the cuprous oxide The case where the particles are respectively bonded to the zeolite substrate; FIG. 6 is a schematic view showing the configuration of a sampling system used for performing biogas gel sampling analysis; and FIG. 7 is a graph illustrating the combination of different content ratios of oxidation The sterilization rate of the adsorption catalyst of copper and zeolite.

Claims (6)

A method for producing an adsorption catalyst combining copper oxide with zeolite comprises the steps of: (i) uniformly mixing a predetermined proportion of cerium oxide with sodium strontium aluminate to form a zeolite component; (ii) forming the zeolite component; a gelling agent is added and mixed to form a colloidal mixture having a slight viscosity; (iii) a predetermined amount of cuprous oxide particle component is added to the colloidal mixture, and mixed with the colloidal mixture, and To uniformly form a gel-like adsorbent premix; (iv) forming the adsorbent premix into a type of adsorbent catalyst preform selected from the following group by a predetermined molding method: strip shape , flakes, powders, spheres and granules; (v) increasing the temperature to 100 ° C ~ 150 ° C by gradually increasing the temperature, and introducing air or nitrogen to the step (iv) under these conditions The prepared adsorption catalyst preform is dried; and (vi) the step (v) dried adsorption catalyst preform is calcined at a temperature of 105 ° C to 450 ° C for 1 to 3 hours. After the calcination time, an adsorption catalyst combining copper oxide with zeolite is obtained. The method for producing an adsorption catalyst comprising cuprous oxide and zeolite according to claim 1, wherein in step (i), the weight ratio of cerium oxide to sodium lanthanum aluminate is 65:35. The method for producing an adsorption catalyst for combining cuprous oxide and zeolite according to claim 1, wherein in the step (ii), the gelling agent is A substance selected from the group consisting of sodium hydroxide, sulfuric acid, hydrochloric acid, and water. A method for producing an adsorption catalyst comprising cuprous oxide and zeolite according to claim 3, wherein in the step (ii), the gelling agent is substantially sodium hydroxide having a concentration of 0.75N. The method for producing an adsorption catalyst for combining cuprous oxide and zeolite according to claim 1, wherein in the step (iii), the cuprous oxide particle component in the adsorbent premix is The zeolite component is mixed in a weight ratio of 1:99 to 50:50. The method for producing an adsorption catalyst for combining cuprous oxide and zeolite according to claim 5, wherein in the step (iii), the cuprous oxide particle component in the adsorbent premix is The weight ratio of the zeolite component mixture is substantially from 3:97 to 5:95.