TW201414539A - Removing volatile organic compounds plate catalyst, method for producing the same and application thereof - Google Patents

Abstract

A plate catalyst for removing volatile organic compounds (VOCs), a method for producing the same and application thereof are disclosed. Copper salt, manganese salt, titanium dioxide, clay, inorganic fibers and water are mixed to form catalyst material. Then, the catalyst material is rolled on a metal net, and subsequently undergoes thermal treatment process to form the plate catalyst for removing VOCs.

Description

Plate-shaped catalyst for removing volatile organic compounds, manufacturing method thereof and application thereof

The present invention relates to a catalyst, and more particularly to a plate-like catalyst for removing volatile organic compounds, a method for producing the same, and an application thereof.

In recent years, in the industry of steel mills or sintering plants, there are often volatile organic compounds (VOCs) in the exhaust gas. Volatile organic compounds are harmful to humans and other organisms, which will cause an environment. Pollution. With the rise of environmental awareness, industry must shoulder its social responsibilities, so it is necessary to remove VOCs before exhaust emissions.

In order to remove VOCs, conventional techniques have developed a catalyst for removing VOCs using precious metals as the main active center. However, the price of precious metals is not high. In order to reduce costs, the industry is now trying to use transition metals as active centers to develop catalysts for removing VOCs.

Conventional transition metal catalysts are mainly prepared by forming an aqueous solution containing a transition metal in a honeycomb or granular support or substrate by impregnation or coprecipitation. However, this process has the following disadvantages. First, when the catalyst is prepared by means of impregnation or coprecipitation, the active ingredient needs to be used in the aqueous solution for a long time to precipitate on the surface of the support or the substrate. The above process will generate a large amount of waste liquid, which will cause pollution to the environment again.

Secondly, since the exhaust gas generated by the steel mills that have been in operation always has dust, when passing through the conventional honeycomb or granular catalyst, on the one hand, the dust will impact the honeycomb or granular catalyst, causing the transition metal to peel off. Shadow It removes the effect of removing VOCs. On the other hand, dust accumulates between the honeycomb or the particulate catalyst, so that the exhaust gas does not easily flow through the honeycomb or granular catalyst, causing a huge pressure difference, forcing the operation to stop.

In view of this, it is urgent to propose a catalyst for removing VOCs and a method for manufacturing the same, thereby improving various problems caused by conventional catalysts.

Therefore, one aspect of the present invention provides a method for producing a plate-like catalyst for removing VOCs by kneading a copper metal salt, a manganese metal salt, a titanium oxide, a clay, an inorganic fiber, and water into a catalytic material. Thereafter, the catalyst material is formed on the metal mesh by a rolling step and subjected to a heat treatment process to form a plate-like catalyst for removing VOCs. Since the manufacturing method does not need to be disposed in an aqueous solution, the discharge of the wastewater and the time required for the process can be reduced, and thus various problems caused by the conventional catalyst preparation process for removing the VOCs can be improved.

Another aspect of the present invention provides a sheet-like catalyst for removing VOCs which is obtained by the above method.

Yet another aspect of the present invention is to provide a method of removing VOCs characterized in that the plate-like catalyst can remove at least 95% of benzene, xylene or toluene in the exhaust gas.

According to the above aspect of the invention, there is provided a method of producing a plate-like catalyst for removing VOCs. In one embodiment, the method includes providing a catalytic material, wherein the catalytic material comprises at least a copper metal salt, a manganese metal salt, titanium dioxide, clay, inorganic fibers, and water, but no vanadium, tungsten, and molybdenum. Then, the catalyst material is formed on at least one side of the metal mesh by a rolling step, To form a plate-shaped catalyst substrate. Next, the plate-shaped catalyst substrate is subjected to a heat treatment process to form a plate-shaped catalyst for removing VOCs, and the above-mentioned plate-like catalyst is used for removing benzene, xylene or toluene and any combination thereof.

According to an embodiment of the invention, the catalyst material comprises from 20.3 weight percent to 27.6% by weight copper metal salt, from 20.2 weight percent to 28.6 weight percent manganese metal salt, from 33.6 weight percent to 46.3 weight percent titanium dioxide, 2.1 weight percent To 4.1 weight percent clay, 4.1 weight percent to 9.5 weight percent inorganic fibers, and 6.8 weight percent to 18 weight percent water.

According to an embodiment of the invention, the catalyst material comprises 21.7 weight percent to 26.2 weight percent copper metal salt, 21.5 weight percent to 25.4 weight percent manganese metal salt, 35.4 weight percent to 43.1 weight percent titanium dioxide, 2.1 weight percent To 4.1 weight percent clay, 4.3 weight percent to 9.3 weight percent inorganic fibers, and 7.1 weight percent to 14 weight percent water.

According to an embodiment of the invention, the copper metal salt may include, but is not limited to, copper nitrate, copper acetate, and any combination thereof.

According to an embodiment of the invention, the manganese metal salt may include, but is not limited to, manganese nitrate, manganese acetate, and any combination thereof.

According to an embodiment of the invention, the atomic ratio of copper to manganese is 1:1 to 1:5.5. In another embodiment, the atomic ratio of copper to manganese is 1:1 to 1:2.

According to an embodiment of the invention, the material of the clay is an aluminum-containing niobium oxide. In another embodiment, the material of the inorganic fiber is cerium oxide. In still another embodiment, the metal mesh is made of stainless steel.

According to an embodiment of the invention, the heat treatment process described above comprises a drying step and a calcining step. In one example, the temperature of the drying step described above is from 100 to 150 °C. In another illustration, the calcination step described above has a temperature of from 300 to 500 °C.

According to another aspect of the present invention, there is provided a plate-like catalyst for removing VOCs which is obtained by the above method.

According to still other aspects of the present invention, there is provided a method of removing VOCs characterized in that the plate-like catalyst is capable of removing at least 95% of benzene, xylene or toluene in the exhaust gas.

Regarding the plate-shaped catalyst for removing VOCs of the present invention, and a method and a method for producing the same, the catalyst material is kneaded and mixed, and then subjected to a heat treatment process to obtain a plate-like catalyst for removing VOCs. Since this manufacturing method does not need to be disposed in an aqueous solution, the discharge of wastewater and the time required for the process can be reduced. Further, the plate-like catalyst obtained by the production method of the present invention can remove at least 95% of benzene, xylene or toluene in the exhaust gas.

As described above, the present invention provides a plate-like catalyst for removing VOCs, a manufacturing method thereof and an application thereof, wherein a catalyst material is formed on at least one side of a metal mesh by a rolling step, and then subjected to a heat treatment process to form a removal. Plate-like catalyst for VOCs.

Catalytic material

The catalyst material of the present invention has a transition metal as an active center. In an embodiment, the catalyst material of the present invention comprises at least a copper metal salt, Manganese metal salts, titanium dioxide, clay, inorganic fibers and water, but no vanadium, tungsten and molybdenum.

In one embodiment, the catalyst material comprises from 20.3 weight percent to 27.6 weight percent copper metal salt, from 20.2 weight percent to 28.6 weight percent manganese metal salt, from 33.6 weight percent to 46.3 weight percent titanium dioxide, from 2.1 weight percent to 4.1. Weight percent clay, 4.1 weight percent to 9.5 weight percent inorganic fibers, and 6.8 weight percent to 18 weight percent water.

In one embodiment, the catalyst material comprises from 21.7 weight percent to 26.2 weight percent copper metal salt, from 21.5 weight percent to 25.4 weight percent manganese metal salt, from 35.4 weight percent to 43.1 weight percent titanium dioxide, from 2.1 weight percent to 4.1. Weight percent clay, 4.3 weight percent to 9.3 weight percent inorganic fibers, and 7.1 weight percent to 14 weight percent water.

In an example, the above-mentioned copper metal salt and manganese metal salt are used as an active center. In another illustration, the titanium dioxide described above is a carrier such that the active center can be attached to the support. In still another example, the clay is used as a binder to allow the catalyst material to be rolled onto the metal mesh, and the inorganic fibers are used to increase the strength of the catalyst material to the metal mesh.

In one example, the copper metal salt described above can include, but is not limited to, copper nitrate, copper acetate, and any combination thereof. In another illustration, the manganese metal salt described above may include, but is not limited to, manganese nitrate, manganese acetate, and any combination thereof.

In one embodiment, the copper metal salt and the manganese metal salt have two to four crystal waters, respectively.

In one embodiment, the atomic ratio of copper to manganese described above is a particular ratio. In one example, the atomic ratio of copper to manganese is 1:1 to 1:5.5. In another illustration, the atomic ratio of copper to manganese described above is 1:1 to 1:2.

In one embodiment, the material of the clay described above is an aluminum-containing niobium oxide. In another embodiment, the material of the inorganic fiber is cerium oxide.

Method for manufacturing plate-shaped catalyst for removing VOCs

Please refer to FIG. 1 , which is a flow chart showing a method for manufacturing a plate-shaped catalyst for removing VOCs according to an embodiment of the present invention.

First, as shown in step 110, a metal mesh is provided. In an embodiment, the material of the metal mesh may include, but is not limited to, stainless steel.

Next, as shown in step 130, the catalyst material is subjected to a kneading step, wherein the catalyst material is as described above, and will not be further described. In one embodiment, titanium dioxide, a copper metal salt, and a small amount of water are first placed in a kneading device for kneading for 1 to 3 hours. Then, the manganese metal salt is mixed with a small amount of water, and then added to a kneading device, and kneading is carried out for 1 to 3 hours. Subsequently, the inorganic fibers are added to the kneading device, and kneading is carried out for 2 to 4 hours. Subsequently, the clay is added to the kneading device, and kneading is carried out for 2 to 4 hours to form a catalyst material.

Further, as shown in step 150, the above-mentioned catalyst material is formed on the metal mesh by a rolling step to form a plate-shaped catalyst substrate, wherein the coating amount per unit area (cm ² ) of the catalyst material is 0.1 gram to 0.15 gram.

Subsequently, as shown in step 170, the plate-like catalyst substrate is subjected to a heat treatment process. In one embodiment, the heat treatment process described above comprises a drying step and a calcining step. In one example, the temperature of the drying step described above is from 100 to 150 ° C for 1 to 3 hours. In another illustration, the calcination step described above is carried out at a temperature of 300 to 500 ° C for 3 to 5 hours.

It is worth mentioning that one of the features of the method of the present invention is to discard the conventional impregnation method or the coprecipitation method, and the catalyst material is kneaded and mixed, and then subjected to a heat treatment process to obtain a plate shape for removing VOCs. catalyst. Since this manufacturing method does not require the catalyst to be disposed in the aqueous solution, the discharge of the wastewater and the time required for the process can be reduced.

Application of plate-like catalyst for removing VOCs

When the plate-shaped catalyst obtained by the method of the present invention is used for removing VOCs, at least 95% of benzene, xylene or toluene in the exhaust gas can be removed.

The following is a few examples to illustrate in more detail the VOCs-removing plate-like catalyst of the present invention and a method for manufacturing the same, which are not intended to limit the present invention, and therefore the scope of protection of the present invention is attached to the patent application. The scope is defined.

EXAMPLES: Preparation of plate-like catalyst for removing VOCs Example 1

In this embodiment, 543 g of titanium dioxide, 324 g of copper nitrate and a small amount of water were placed in a kneading apparatus in that order, and kneading was carried out for 1 to 3 hours to form a first mass. Then, 325 g of manganese nitrate was mixed with a small amount of water, and then kneaded by a kneading device and mixed for 1 to 3 hours to form a second mass. Subsequently, 143 g of inorganic fibers were placed in a kneading device and kneaded for 2 to 4 hours. Subsequently, 45 g of clay was placed in the kneading device and kneaded for 2 to 4 hours to form a catalyst material in which the water content of the catalyst material was 220 g.

Next, the bulk material is coated with a coating roller, for example A stainless steel metal mesh is used to form a plate-shaped catalyst substrate.

Then, the plate-shaped catalyst substrate is subjected to a heat treatment, and a drying step is performed at a temperature of 100 to 150 ° C for 1 to 3 hours, followed by a calcination step, and a temperature of 300 to 500 ° C is carried out for 3 to 5 hours to form a release. A plate-like catalyst other than VOCs.

Thereafter, the VOCs removing catalyst on the metal mesh was scraped off to form a particulate VOCs-removing catalyst, which was used as an activity test.

Examples 2 to 8

The method for producing the VOCs-removing catalyst of Example 1 differs in that Examples 2 to 8 are used to change the amount of components used and the temperature and time of heat treatment, and the formulation thereof is shown in Table 1.

Evaluation method 1. Test system for removing VOCs from catalysts

The VOCs flue gas (hereinafter referred to as reaction gas) of the simulated industrial process is passed to the test system for removing VOCs in the catalyst of FIG. 1 to evaluate the removal efficiency and reaction of VOCs in the above Examples 1 to 8. Temperature is an assessment of the efficiency of catalyst removal VOCs.

Please refer to FIG. 2, which is a partial schematic diagram showing a test system for removing VOCs by a catalyst according to an embodiment of the invention. The test system 200 for removing the VOCs by the catalyst includes a tubular quartz glass reaction tube 205, a reactor 207, a temperature controller 209, a VOCs heating bottle 211, a buffer bottle 213, a cryogenic collection bottle 215, and a gas phase chromatography analyzer 217.

When testing the ability to remove VOCs, first weigh 1 gram (g) The particulate catalyst 201 for removing VOCs is placed in a quartz glass reaction tube 205 having a length of 55 cm and a diameter of 2.0 cm, a catalyst filling height of about 6.0 cm, and a quartz containing the above-mentioned particulate catalyst 201. The glass reaction tube 205 was placed in a reactor 207 (heater), and the ability to remove VOCs of Examples 1 to 8 was tested.

The aforementioned temperature controller 209 is coupled to the reactor 207 to control the reaction temperature in the reactor 207. The aforementioned quartz glass reaction tube 205 has an inlet end 219a and an outlet end 219b, wherein the inlet end 219a is connected to the buffer bottle 213 via a line 225a. Buffer bottle 213 is connected to VOCs heating bottle 211 via line 225b, wherein VOCs heating bottle 211 is used to house organic compounds.

The nitrogen source 221 can provide the gas required for the VOCs to heat the vial 211 via line 225c. Air source 223 can provide the gas required to buffer bottle 213 from line 225d.

Before the test, the VOCs heating bottle 211 is heated to volatilize VOCs (e.g., benzene, toluene, xylene) into a gas, and then nitrogen gas from the nitrogen source 221 is mixed with the VOCs gas via line 225c to form a first gas. The first gas is then introduced into the buffer bottle 213 via line 225b, and the air from the air source 223 is mixed with the first gas in the buffer bottle 213 via line 225d to form a reaction gas. The line 225b is covered by a heating device 227 for maintaining the temperature of the line 225b.

During the test, the reaction gas in the buffer bottle 213 is introduced into the quartz glass reaction tube 205 via the line 225a to perform the catalyst removal VOCs reaction, wherein the line 225a is covered by the heating device 227 to maintain the temperature of the line 225a. .

In the catalyst removal VOCs test, the reaction temperature is slowly raised from room temperature to a predetermined reaction temperature, and the catalyst is subjected to the removal reaction of VOCs at the reaction temperature.

The aforementioned outlet end 219b is connected to the cryogenic collection bottle 215 for cooling the reacted gas and adsorbing excess moisture. Additionally, the cryogenic collection bottle 215 at the outlet end 219b of the reactor 207 is coupled to a gas chromatography layer analyzer 217, such as a gas phase chromatography analyzer with a flame ionization detector (FID) ( Gas chromatography; GC) (Model No. 6890; Agilent), the concentration of VOCs in the reactants and products was sampled and compared with the concentration of unreacted VOCs at the time of feeding, thereby calculating the catalyst-to-VOCs. Remove efficiency.

The composition of the above reaction gas is 1 to 5 volume percent (vol%) of VOCs, 500 ppm of sulfur dioxide and 2.7 to 3 vol% of water vapor, the gas space flow is 5000 hr ^-1 , and the reaction temperature is 300 ° C to 325 ° C. The reaction time was 4 hours.

2. Evaluate the efficiency of catalyst removal of VOCs

The removal efficiency of the catalyst for VOCs is based on the definition of the following formula (I):

A : percentage of feed volume of VOCs

B : percentage of discharge volume of VOCs

2.1 Evaluation of the efficiency of catalyst removal VOCs

It can be seen from the evaluation results of Table 1 that the above-mentioned plate-like catalyst is in reaction temperature. The degree is from 300 ° C to 325 ° C, and after reacting for 4 hours, at least 95% of benzene, xylene or toluene in the exhaust gas can be removed.

2.2 Evaluation of the reaction temperature for the efficiency of catalyst removal VOCs

Referring to Fig. 3, it can be seen from the evaluation results of Fig. 3 that the removal efficiency of toluene, xylene and benzene in Example 2 was 60% to 70% at a reaction temperature of 200 °C. At a reaction temperature of 260 ° C, the removal efficiency for toluene, xylene or benzene is 90% to 95%. At the reaction temperatures of 300 ° C and 320 ° C, the removal efficiency for toluene, xylene or benzene is more than 95%, and with the increase of the reaction temperature, the removal efficiency for toluene, xylene or benzene also increases.

3. Catalyst strength test system

Since the catalyst in the sintering workshop is easily peeled off due to dust impact, the plate-like catalyst must be tested in the catalyst strength, and the catalyst weight loss must be less than 0.7 g (g).

The area of the plate-like catalyst test piece was 10 cm (cm) × 10 cm, and the thickness of the test piece was 0.8 to 1.0 mm (mm), and the catalyst strength test was performed using a table type sand blasting machine (Mega SBC-110). The test conditions are blasting pressure of 2.0 kg/cm ² , the sand material is glass sand, the particle size is 50-105 micrometers (μm), the distance between the center point of the test piece and the nozzle is 120 mm, and the plane of the test piece is 12 degrees with the blasting airflow. angle.

Table 1 lists the results of the composition and catalyst strength test of each of the plate-like catalyst materials of the respective examples. Among them, the "○" surface catalyst weight loss is less than 0.7 grams.

It can be seen from the test results of Table 1 that the plate-like catalysts are subjected to catalyst strength. After the test, the catalyst weight loss is less than 0.7 gram, which is tested by the catalyst strength and can be applied to industrial processes such as sintering workshops with dust.

In summary, the plate-shaped catalyst for removing VOCs according to the present invention, and a method and a method for manufacturing the same, wherein the catalyst material is kneaded and mixed, and then subjected to a heat treatment process to obtain a plate-shaped catalyst for removing VOCs. . Since this manufacturing method does not need to be disposed in an aqueous solution, the discharge of wastewater and the time required for the process can be reduced. Further, the plate-like catalyst obtained by the production method of the present invention can remove at least 95% of benzene, xylene or toluene in the exhaust gas. Moreover, the plate-shaped catalyst for removing VOCs of the present invention has good catalyst strength and can withstand the impact of dust in industrial processes.

However, it should be added that the present invention is exemplified by specific components, specific reaction conditions, specific analysis methods, specific tests or specific equipments, etc., and illustrates the VOCs-removing plate-shaped catalyst of the present invention, a manufacturing method thereof and application thereof. However, it is to be understood by those skilled in the art that the present invention is not limited thereto, and the VOCs-removing plate-shaped catalyst of the present invention and its manufacturing method and application are not deviated from the spirit and scope of the present invention. Other ingredients, other reaction conditions, other analytical methods, other tests, or other equivalent equipment may also be used.

The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.

100‧‧‧ method

110‧‧‧Steps to provide metal mesh

130‧‧‧Steps for forming the catalyst material by the kneading step

150‧‧‧Steps of forming the catalyst material on at least one side of the metal mesh using a rolling step

170‧‧‧Steps for heat treatment to form plate-like catalyst for removal of VOCs

200‧‧‧ system

201‧‧‧Particulate catalyst

205‧‧‧Quartz glass reaction tube

207‧‧‧Reactor

209‧‧‧temperature controller

211‧‧‧VOCs heating bottle

213‧‧‧buffer bottle

215‧‧‧Cryogenic collection bottle

217‧‧‧ gas phase chromatography analyzer

219a‧‧‧ entrance end

219b‧‧‧export end

221‧‧‧Nitrogen source

223‧‧ Air source

225a/225b/225c/225d‧‧‧ pipeline

227‧‧‧ heating device

The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; A flow chart of a method of manufacturing a catalyst.

2 is a partial schematic diagram of a test system for the ability of a catalyst to remove VOCs in accordance with an embodiment of the present invention.

Figure 3 is a graph showing the removal efficiency of the catalyst for VOCs at different reaction temperatures according to an embodiment of the present invention.

100‧‧‧Manufacturing method of plate-like catalyst for removing VOCs

110‧‧‧Steps to provide metal mesh

130‧‧‧Steps for forming the catalyst material by the kneading step

150‧‧‧Steps of forming the catalyst material on at least one side of the metal mesh using a rolling step

170‧‧‧Steps for heat treatment to form plate-like catalyst for removal of VOCs

Claims (15)

A method for producing a plate-shaped catalyst for removing volatile organic compounds, comprising: providing a catalyst material, wherein the catalyst material comprises at least a copper metal salt, a manganese metal salt, titanium dioxide, clay, inorganic fibers, and water, but not Vanadium, tungsten and molybdenum; the catalyst material is formed on at least one side of a metal mesh by a rolling process to form a plate-shaped catalyst substrate, and a heat treatment process is performed on the plate-shaped catalyst substrate to A plate-like catalyst for removing volatile organic compounds is formed, wherein the plate-like catalyst is used to remove a group of benzene, xylene, toluene, and any combination thereof. The method for producing a volatile organic compound-containing platy catalyst according to claim 1, wherein the catalyst material comprises 20.3 wt% to 27.6 wt% of a copper metal salt, and 20.2 wt% to 28.6 wt%. The manganese metal salt, 33.6 weight percent to 46.3 weight percent titanium dioxide, 2.1 weight percent to 4.1 weight percent clay, 4.1 weight percent to 9.5 weight percent inorganic fibers, and 6.8 weight percent to 18 weight percent water. The method for producing a volatile organic compound-containing platy catalyst according to claim 1, wherein the catalyst material comprises 21.7 wt% to 26.2 wt% of a copper metal salt, and 21.5 wt% to 25.4 wt%. Manganese metal salt, 35.4% by weight to 43.1% by weight of titanium dioxide, 2.1% by weight to 4.1% by weight Soil, 4.3% by weight to 9.3% by weight of inorganic fibers and 7.1% by weight to 14% by weight of water. The method for producing a volatile organic compound-containing platy catalyst according to claim 1, wherein the copper metal salt is selected from the group consisting of copper nitrate, copper acetate, and any combination thereof. . The method for producing a volatile organic compound-containing platy catalyst according to claim 1, wherein the manganese metal salt is selected from the group consisting of manganese nitrate, manganese acetate, and any combination thereof. Ethnic group. The method for producing a volatile organic compound-containing platy catalyst according to claim 1, wherein the atomic ratio of the copper to the manganese is 1:1 to 1:5.5. The method for producing a volatile organic compound-containing platy catalyst according to claim 1, wherein the atomic ratio of the copper to the manganese is 1:1 to 1:2. A method for producing a volatile organic compound-containing platy catalyst according to claim 1, wherein one of the clay materials is an aluminum-containing cerium oxide. Removal of volatile organic compounds as described in item 1 of the patent application A method for producing a platy catalyst of the object, wherein one of the inorganic fibers is cerium oxide. The method for producing a volatile organic compound-containing plate-like catalyst according to the first aspect of the invention, wherein the metal mesh is made of stainless steel. The method for producing a volatile organic compound-containing platy catalyst according to claim 1, wherein the heat treatment process comprises a drying step and a calcining step. The method for producing a volatile organic compound-containing platy catalyst according to claim 11, wherein the drying step has a temperature of 100 to 150 °C. The method for producing a volatile organic compound-containing platy catalyst according to claim 11, wherein the calcination step has a temperature of 300 to 500 °C. A plate-like catalyst for removing volatile organic compounds, which is produced according to the method of any one of claims 1 to 13. A method for removing volatile organic compounds, characterized in that the removal rate of benzene, xylene or toluene by a plate-like catalyst for removing volatile organic compounds according to claim 14 of the patent application is greater than 95%.