TWI293036B - Catalyst, method for producing the same and method for treating volatile organic compounds - Google Patents

Description

1293036 ‘ Nine, invention description: [Technical field to which the invention pertains] The present invention relates mainly to an environmental engineering technique, and more particularly to a catalyst for treating volatile organic compounds. [Prior Art] • With the rapid development of industry and commerce, the problem of environmental pollution is increasing. The problems caused by air pollution are very serious, such as NOx, SOx, and Volatile Organic Compounds (VOCs). Volatile organic compounds are organic compounds which are steamed at a standard pressure (2〇c>c, 76〇mmHg) and have a gas pressure greater than 0·1 mmHg. The carbon chain length is usually between C2 and C6. In short, volatile organic compounds are low-polar, low-boiling, volatile organics that are often released into the environment by many industrial activities such as the petrochemical surface coating industry and steam locomotive emissions. Volatile organic compounds include (1) gas-containing hydrocarbons, (7) aromatic chlorocarbon compounds, (3) monoalcohols (monoa c〇h〇ls) or polyalcohols (p〇iyaic_is) and (4) Ψ _ . Petroleum, pesticides, solvents, chemical raw materials, etc. are common volatilization ‘ ^ organic products. Volatile organic compounds derived from organic solvents such as phenyltoluene isopropanol, diethylene oxide, etc. are also currently harmful air pollutants. Volatile organic compounds are carcinogenic, mutagenic and teratogenic to humans and cause harm to human skin, central nervous system, eyes, respiratory tract, and internal organs. Furthermore, 'volatile organic compounds are precursors for the formation of atmospheric photochemical smog'. Volatile organic compounds and strontium are irradiated by ultraviolet light, which in turn can produce ozone and peroxyacetoxy nitrate (ΡΑΝ), which is irritating and dangerous to human body.

O:\103\103498.DOC -6 - 1293036 It is very harmful. At present, the treatment technology of volatile organic compounds can be divided into two categories: recyclability and destructive treatment. Recycling treatment technologies include physical absorption method, adsorption method, condensation method and vapor balance method. Destructive treatment technology includes ·· Treatment, chemical absorption and thermal incineration. Both the adsorption and absorption methods in the sputum will cause liquid and solid secondary pollutants. The biological treatment method is a lower cost treatment method, but it is still limited by the difference between the treatment efficiency of pollutants and the inflow of pollutants. The thermal incineration law has no such concerns, and the combustion methods include catalytic incineration, direct incineration, and regenerative incinerator incineration (RT〇). Catalyst incineration is one of the most widely used methods in the industry. It uses catalyst to catalyze the oxidation of pollutants in exhaust gas, increase the reaction rate and lower the reaction temperature to 20〇QC to 400〇C. 〇〇 to 1〇〇〇mg/m3 and the flow rate is higher than 5〇〇m3/hri waste exhaust, which has the advantages of lower operating temperature, less energy incineration, less energy consumption, and better pollutant destruction efficiency. If the exhaust gas contains a poisoning catalyst, it should be removed before treatment to avoid poisoning of the catalyst. In addition, fouling, sintering, damage, and disappearance of active ingredients may cause the activity to decline. The composition of the catalyst is mainly a single or mixed metal as an active center, and the active center increases the processing efficiency by attaching to the carrier to increase the contact area with the processing gas. The types of catalysts used today for catalytic combustion are generally classified into precious metals and general metal oxides. Different types of catalysts are also different for the treatment effect and the exhaust gas suitable for treatment. Valuable metals include platinum (pt), palladium (Pd), gold (Au), silver (Ag), etc., and often form alloys with bismuth (Os), iridium (Ir), ruthenium (Ru), money (Rh), and the like. Its activity is better than general metal oxides.

O:\103\103498.DOC -7- 1293036 The contaminant has a good conversion rate at low temperatures, and the carrier is mostly a metal oxide. However, in the practical application, precious metals are expensive, the production is scarce, easy to k: the volatiles are easily lost, and in the air pollution control equipment, precious metals are easily poisoned to inhibit the treatment effect, and further, catalyst catalytic The reaction is selective. If the composition of the reaction species is complex, its efficiency is not good. Even if it touches, it can catalyze the formation of reactants, which may cause the components of the reactants to be unstable or still produce harmful substances. Looking at the carrier part, in theory almost any substance can be used as a carrier of the catalyst, but generally it is limited to a small number of specific substances, such as cerium oxide, aluminum oxide, titanium oxide, zeolite, activated carbon and the like. However, the carrier is usually selected depending on the requirements of the reaction or the process, such as the mechanical strength, shape, surface area, and acidity of the carrier. In catalyst incineration, the main carrier is usually a metal oxide. However, the general metal oxide carrier is expensive and increases the cost of processing V〇CsJl, which is a limiting factor in the development of catalysts. It is still necessary for the industry to develop - low-cost, stable and highly efficient catalysts. SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst comprising: an active center comprising a copper metal or a steel oxide; and a carrier for attaching the active center and having the following characteristics: (0 Heat resistant to 100 to 1,000 ° C; (ii) specific heat from 750 to 950 J / kg -0c;

O:\103\103498.DOC -8 - 1293036 (out) thermal conductivity is from 1 to 3 w/m-°C; (iv) particle surface area is from 3 to 7 cm2; (v) specific surface area is from 400 to 700 ηΓ1 ; and (vi) The filling porosity is from 〇·2 to 〇·6. Another object of the present invention is to provide a method of producing the above catalyst, the method comprising the steps of: (a) providing the carrier; (b) providing a solution containing copper metal or copper oxide; (c) providing the carrier with The solution containing copper metal or copper oxide is mixed and impregnated; (d) drying the product obtained in the step (c); and (e) :): burning the product obtained from (d) to obtain the catalyst. A further object of this volume is to provide a method of treating volatile organic compounds with the aforementioned catalyst. [Embodiment] The present invention provides a catalyst comprising: an active center comprising copper metal or copper oxide; and a carrier 'for attaching the active center, 1 having the following characteristics (0 heat resistant 100 to 1) , 〇〇〇0C; (η) specific heat is from 750 to 950 J / kg, c; (nO thermal conductivity is from 1 to 3 W / m - 〇c; (iv) particle surface area is from 3 to 7 cm2; (v) The specific surface area is from 400 to 700 m_i; (vi) The filling porosity is from 0.2 to 0.6. The catalyst of the present invention is a copper-collecting metal or a copper oxide as an active center.

O:\103\103498.DOC -9- 1293036 The steel metal used in the present invention is not a precious metal, and the cost of manufacturing the catalyst can be greatly reduced, and the conversion rate is as high as 95%. In the present invention, the weight ratio of the steel metal and the copper oxide to the catalyst is from 1 to 30%, preferably from 3 to 1% by weight. In an embodiment of the invention, the active center further comprises cobalt metal or cobalt oxide; the weight ratio of cobalt metal and cobalt oxide to the catalyst is 1 to 3%, preferably 3 to 10%, copper. Metal or copper oxide can be combined with cobalt metal or cobalt oxide in any molar ratio, but the molar ratio of copper metal or steel oxide to cobalt metal or cobalt oxide is higher due to the higher cost of cobalt metal. Good for 9:1 to 5:5; better for 8:2 to 6:4. The term "carrier" as used herein means a material to which a metal of an active center or an oxide thereof is attached, which has a porous state, so that an active center: a metal or an oxide thereof can be uniformly distributed thereon, and the reaction is increased. Contact area 'and increase the mechanical properties of the catalyst such as wear resistance, hardness, and M strength, and have heat storage characteristics. The carrier is not limited to a particular substance, but catalysts having different carriers have different reaction efficiencies. According to the carrier of the present invention, the metal of the active metal or its oxide can be uniformly dispersed, and the sintering of the metal due to the too dense bonding of the metal of the active center or its oxide is prevented, resulting in a decrease in surface area. Reduce the effectiveness of the reaction. In general, a person of ordinary skill in the art to which the present invention pertains may select an appropriate carrier for consideration of surface area, mechanical strength, porosity, cost, and stability. On the other hand, T further considers the interaction between the carrier and the metal t, which also affects the catalytic activity and selectivity of the catalyst. Preferably, the average density of the carrier according to the present invention is from 2,500 to 2, _Kg/m3; on the other hand, the average particle diameter of the carrier according to the present invention is from 〇5 to 〇 U3 U on the one hand, 乂

O:\103\103498.DOC -10- 1293036 According to the present invention, the particle sphericity is from 0 · 5 to 〇. In a specific embodiment of the invention, the carrier is a thermal stone having the above characteristics. The heat storage stone can be taken from the grade stone of general building materials. When the temperature is between (4) and 1,1, it has a relatively high heat storage capacity. When it is used for incineration of the regenerative catalyst, it can save energy and has a low price. Get the advantage of the party. This is another method for manufacturing a catalyst according to the present invention, the method φ comprising the steps of: (a) providing the carrier; (b) providing a solution containing copper metal or copper oxide; - (4) providing the carrier with a solution containing copper metal or copper oxygen (tetra) is mixed and impregnated; _ (d) drying the product obtained in the step (c); and removing the product obtained from the product (d) to obtain the catalyst. The method of the present invention, wherein the carrier of the step (4) can be selected by a person having a general knowledge in the technical field of the present invention as needed. • When the field uses the heat storage stone as a carrier, the sieve can be used to screen the heat storage stone. Preferably, the step (4) further comprises pickling and/or washing the carrier, and if necessary, washing the carrier with water. According to the method of the invention, wherein the step (8) contains copper metal or copper oxide. The solution is preferably a metal nitrate solution. According to the invention, the mixed impregnation of step (e) can be carried out by a sedimentation method, a coprecipitation method, an impregnation method, a vapor impregnation method, a critical impregnation method or an ion exchange method. - Embodiment, in which the towel ⑷ step of mixing good DETAILED DESCRIPTION

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-11 - 1293036 The impregnation system is subjected to a steam impregnation method in which a carrier is impregnated with a solution containing copper metal or copper oxide, and the solution is usually an aqueous solution, and then the carrier is dried and prepared. It is preferred to use copper silicate, which is ancient and water-soluble and inexpensive. The mixed impregnation is continued for at least 12 hours, preferably at least 20 hours. The catalyst prepared by the vapor impregnation method has the following (4) 疋 (1) uniform mixing of each of the forming knives with a molecular scale (2) 'The catalyst particles are evenly distributed; (3) The size and shape of the catalyst are not affected by the shape of the carrier; and (4) the pore size and pore size distribution can be effectively controlled. Preferably, the step (b) further comprises providing a solution containing the starting metal oxide; and the step (4) further comprises: charging the carrier with a liquid containing a starting metal or a metal oxide/amp; More preferably, the solution containing the cobalt metal is a cobalt nitrate solution. Step (4) may include a charming agent, a slip agent, and an additive generally used to manufacture a catalyst, as needed. Optionally, the present invention is carried out in the step ((Afterwards, a washing step may be additionally included, which removes impurities or electrolytes from the catalyst component. The decanting method may use decantation (deCantatl〇n) or filtration). The washing liquid is mostly deionized water, and sometimes it can be carried out using an acid solution or an alkali solution. According to the method of the present invention, the drying step of the step (4) is carried out at 8 to 120 ° C, preferably 100 to U〇CT is dried at a temperature of 8 hours, preferably at least 10 hours, more preferably 24 hours or more. It removes moisture from the pores or forms an insoluble precipitate of the metal salt to obtain a certain value. Physical characteristics. According to the method of the present invention, in the calcining step of step (d), the /jnL degree required for the calcination needs to reach at least the temperature at which the catalyst is used, and at the same time

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Gas, nitrogen, hydrogen, etc., if necessary, may be passed through a gas such as steam, carbon monoxide or hydrogen sulfide, which is preferably calcined under an inert atmosphere. Preferably, the calcination is carried out by heating to 8 to 9 skips for 4 hours or more. The simmering simmer has the following functions: (1) removing (iv) the binder, lubricant, salt and useless organic matter; (2) increasing the contact hardness without reducing the surface area; (7) forming the desired oxide type of the metal salt (4) a metal oxide or a lower valence compound when reacted with hydrogen; (5) controlling the initial activity of the catalyst; (6) increasing the force between the metal and the support; and (7) increasing the metal on the support. Dispersion. The catalyst of the invention has good catalytic activity, can be applied to the oxidation catalytic reaction of volatile organic compounds, has extremely high conversion rate, and can greatly reduce the cost of manufacture' and can effectively reduce environmental pollution impact, and is quite in line with environmental protection requirements. . The catalyst according to the present invention can be used to treat volatile organic compounds, that is, the catalyst of the present invention can be used to treat: (1) gas-containing hydrocarbons, (2) aromatic hydrocarbons, (3) monoalcohols or polyalcohols. With (4) ketones. In one embodiment of the invention, it is used to treat isopropyl alcohol. The catalyst of the present invention is very efficient in removing gaseous volatile organic compounds, and the main products are carbon dioxide and water, which can effectively reduce pollution impact and meet environmental protection requirements. Mao Ming also provides a method for treating volatile organic compounds, which is based on the catalyst of the present U. According to the present invention, the method of treating volatile organic compounds is a catalyst incineration method, preferably a regenerative catalyst incineration method. The susceptibility method utilizes a catalyst to catalyze the oxidation of volatile organic compounds, increase the reaction rate and lower the reaction temperature. In the method of the present invention, the treatment temperature is 1 〇 (

O:\103\103498.DOC •13· 1293036 to 1,000. Oh, preferably from 250 to 350. Hey. The conversion rate of the catalyst treatment is related to the inflow temperature, the influent oxygen concentration, the influent concentration and the spatial flow rate, which increases with the inflow 1 degree and the influent oxygen concentration, but with the influent concentration and the spatial flow rate. On the other hand, the reaction rate is related to the reaction temperature, the influent oxygen concentration and the influent concentration. When the influent concentration is larger, the reaction temperature is higher, and the oxygen influx concentration is higher, the reaction rate is larger. Therefore, according to the method of the present invention, the influent concentration of volatile organic compounds is from 100 to 5,000 ppm, preferably from 600 to 2,500 PPm; the oxygen influent concentration is from 20 to 50%, preferably from 30 to 40%; 2,000 to 20,000 hr·1, preferably 3,000 to 7, 〇〇() hr.1 The following examples are intended to illustrate the invention in detail, and are not intended to limit the invention to the disclosure. Example 1: Preparation of Catalyst This example uses a regenerative stone as a carrier, and the copper metal or copper and the initial mixed metal are supported by a vapor impregnation method, and then subjected to a process such as drying and simmering to prepare an oxidized copper-containing material. Catalyst or copper-cobalt catalyst, load 3 of metal catalyst: 3%, 5%, and 1%, respectively, and the molar ratio of steel and cobalt is 8 ·· 2, 7 · 3, 6 · 4 and Pure copper. The physical properties of the regenerative stone are shown in Table 1 below. Table 1: Project value specific heat 840 J/kg-°C Thermal conductivity coefficient moxibustion S 1.9 W/m-°C Average particle size office 0.01 m O:\103\103498. DOC -14- 1293036 Average density p ^ 2615 Kg/m3 Particle surface area A 4.8 cm2 Specific surface area α 540 ηΓ1 Particle sphericity 0 S 0.65 Filled porosity ε 0.415 1·Filled porosity (ε) Place the stone in a one liter beaker to Filled and filled with water, the water level will not drop after standing for a long time. At this time, it means that the disc stone has reached water saturation, then adjust the beaker water level to the scale of - liter, take out the stone, measure the volume of water in the beaker, eight The volume fraction of the liter beaker is the porosity. 2·Average particle size (φ) Calculate the number N of gravel in the above one liter volume to estimate the average particle dp(m) 〇^ ^=[6(1- ε )/1〇〇〇Νπ]ι/ 3 3. Average Density (ps) The above-liter-liter volume of the disc stone is dried to remove water, and then cooled to room temperature to obtain its weight W (kg), and the average density of pH kg/m3) can be determined. P s = 1000[W/(1- ε )] 4·Particle surface area The above-mentioned gravel is randomly taken from several samples, and the (iv) paper weight and the unit area (four) paper weight are mutually coated by the (4) paper single layer. Estimate the surface area of the particles. Λ '5·particle sphericity)

O:\103\103498.DOC -15- 1293036 Particle sphericity is defined as "the surface area of the sphere of the same volume / the true surface area of the pellet". φ s^{Tidp2)l{Sa) 6. Specific surface area (α) The specific surface area is the surface area of the stone per unit filling volume. «=[6(1- ε )]/(dp φ s) - The catalyst preparation steps are as follows: φ (1) The regenerative stone is washed and immersed in a 5% nitric acid solution for 1 hour. After soaking, use water to thoroughly oscillate and clean. Then, after soaking for 2 hours with 2.5% sodium hydroxide lye, it is also cleaned with water. Finally, it is rinsed with pure water and placed in an oven to avoid contact with grease or other chemicals. (2) Take (1) the treated regenerative stone (for example, 9〇g) and place it in a beaker. The carrier mother size is about 〇5 to 1 cm3. (3) Take the copper nitrate and nitric acid # to be configured (for example, the loading ratio is 1%, the molar ratio of copper to cobalt is 6:4, the copper nitrate is added, and the cobalt and cobalt are added to 17g). Add 50 ml of pure water to dissolve completely. (4) The prepared drug (3) was placed in a glass beaker placed with a carrier, and the amount of water was slightly longer than the carrier. After impregnation for 24 hours, the beaker was placed on a heating plate to evaporate water. (5) After the impregnation liquid has evaporated, place the catalyst precursor in the tank for about 24 hours. (6) Put the initial catalyst into the sintering furnace and simmer it at a flow rate of 4 L/min, and raise the temperature according to the temperature program. c stops (four) minutes, then heats up to 600. C after the mother burned for 4 hours, and won the car & and I wait for copper and cobalt catalyst. The simmering equipment is shown in Figure 1.

O: \103\103498.DOC -16 - 1293036, wherein the catalyst 104 to be sintered is placed on the quartz porous separator 103 in the quartz sintered tube 1〇1, and the quartz sintered tube 1〇1 is installed at both ends There is a K_type thermocouple meter 105 and the upper end is a refractory mud cover 107, and a temperature controller u〇& floater 1 meter 109 controls the temperature and gas flow respectively, and is heated by a heating furnace 106, during the burning process The generated exhaust gas is discharged from the waste outlet port 1〇8. It can be seen by scanning electron microscopy (SEM) (see Fig. 2a) that the metal surface is in the form of a cotton batt; surface element analysis (EDS) is also performed, and the results are shown in Fig. 3a, which reveals elements including Cu, Co, Ca, etc. Cii and Co metals are produced by the addition, and Ca is estimated to be the component of the regenerative stone. Example 2: Treatment of Volatile Organic Compounds by Catalyst This example was treated with the catalyst prepared in Example 1 for isopropanol, which was carried out in an apparatus as shown in FIG. In this example, the simulation system of the vapor phase volatile organic compound utilizes four gases such as a volatile organic solution 4〇5, a nitrogen gas (乂) 403, an oxygen gas (〇2) 4〇2, and an air (using an air compressor 4〇1), respectively. It is fed into the reaction system through a separate stainless steel pipeline, and first passed through a filter to remove moisture and impurities that may be contained in the inflow gas to avoid damage to the flow meter 404. Thereafter, each gas is controlled by a float flow meter to control its entry. The flow in the system, where a portion of the nitrogen is used to carry the volatile organic vapor and a portion is used as the system diluent gas. Before the gas enters the catalytic reaction system, it must pass through a gas mixer to uniformly mix the influent emulsion before entering the catalyst reaction system. The humidity is adjusted by using a gas evaporation bottle containing a proper amount of water in a constant temperature water tank, and the water is volatilized at a constant temperature by controlling the water temperature.

O:\103\103498.DOC 8 -17- 1293036 The catalyst reaction system mainly uses the catalyst reaction tube to be heated in a high temperature heating furnace. The reaction tube is made of stainless steel, the length is 90 cm, and the inner diameter is 8·5 cm. The center has a semi-controlled 3.75 cm, 1.5 cm thick stainless steel round mesh 53 to support the catalyst. When the catalyst is placed, a layer of quartz waol 54' is wrapped around the catalyst bed 52 to ensure the stainless steel round mesh and stainless steel. The pipe wall is completely fitted; a K type thermocouple meter 51 is placed directly above the catalyst bed, and the temperature inside the pipe is measured, and the temperature controller is controlled by the temperature controller to control the heating process in the high temperature reactor, and the filling mode of the catalyst bed is shown in the figure. 5. After the influent mixed gas passes through the catalytic reaction system, the gas after the reaction is collected by using a sampling bag, and the gas collected in the sampling bag is analyzed by GC-FID415 for the concentration of isopropyl alcohol. 〇2, the concentration is measured by GC-TCD, or a flue gas monitor can be used. Figure 6 shows the comparison of the conversion of isopropanol at different temperatures for a blank test, a carrier blank test, and a 1% copper-cobalt (mole ratio 6:4) catalyst. The blank effect test is a set of glass wool instead of catalyst with the same catalyst bed volume as the blank test (Blank), and the carrier Blank is the heat storage stone after the same catalyst bed volume. As a test. As can be seen from Fig. 6, Blank, carrier Blank, and copper-cobalt heat-storing stone catalyst were 458 (temperature at a conversion rate of 5〇%) of 458, respectively. (:, 363 ° C, 242 ° C, T95 (conversion rate 95 〇 / 〇 temperature) are greater than 475 ° C, greater than 475 ° C, 350. From the results, the copper cobalt heat storage stone catalyst can be successful The TPs are reduced to 35〇<5C, so the copper-integrated thermal stone catalyst can greatly improve the treatment efficiency of isopropyl alcohol. Example 3: The effect of different metal ratios on the conversion of isopropanol This example uses the heat storage stone as the carrier. , copper, cobalt are active metals, making gold

O:\103\l 03498.DOC • 18 - 1293036 The load (metal/stone) is 3%, 5%, ι〇%, and pure copper and steel surface molar ratio are 8 : 2, 7 : 3, 6 : 4 catalyst. Under the same reaction conditions, the isopropanol influent concentration was 1500 ppm, the space velocity was 135 hrl, and the oxygen influx concentration was 21%, which was tested for its effect on incineration of isopropanol. Figure 7 shows the conversion of isopropanol at different temperatures for a copper catalyst with a loading of 3% and a copper-cobalt molar ratio of 8:2, 7:3, and 6:4, respectively. As can be seen from the figure, the T5 〇 is 358. 313 313. 0 319. (:,, I T95 is greater than 475 ° C, 412 ° C, 463. (:, Figure 8 is a load of 5% of copper catalyst and copper Mo molar ratio of 8: 2, 2, 7: 3,6:4 copper-cobalt catalyst comparison of isopropanol conversion rate at different temperatures. As can be seen from the figure, the T50 is 350〇C, 322〇c, 319〇c, 29()c)e , T95 is greater than 475. (:, 428 ° C, 438. (:, 465. (: Figure 9 is a load of 1 〇% of copper catalyst and copper Mohr ratio respectively $: 2, 7 : 3,6:4 Copper-cobalt catalysts at different temperatures for the conversion of isopropanol. As can be seen from the figure, the butyl 50 is 328. (:, 293. (:, 286. 〇:, 242 (;:, Τ95 is 472 ° C, 425 ° C, 399. (:, 350. (: Figure 1) is a different loading and different metal ratio of the catalyst at different temperatures to isopropanol Comparison of conversion rate. It can be seen from the figure that although the conversion rate of copper catalyst will increase with the increase of the load amount, it is still not enough to add a small amount of catalyst for the base metal. It is indeed possible to increase the conversion of isopropanol. As a result, it is known that the catalyst with a loading of Cong and a copper molar ratio of 6:4 has the best operational performance. Figure 11 shows the conversion of isopropanol and its intermediates at different temperatures at the optimum catalyst. Relationship with the final product, 'I know that isopropyl alcohol will be at low temperatures

O:\103\103498.DOC -19- 1293036 Acetone is formed by itself. When the temperature is slowly heated, it will change back to isopropanol. Finally, it will be incinerated into carbon dioxide and water by the catalyst, so the final concentration of isopropyl pure and acetone Gradually decreasing, the relationship between product concentration and temperature is shown in u. Example 4: Operational parameters for the conversion of isopropanol conversion The metal loading of 10% metal copper and cobalt catalyst (copper-cobalt molar ratio of 6: ▲ 4) is a catalyst with higher conversion rate, in addition to change In addition to the parameters, the other reaction conditions were isopropanol influent concentration of 1,500 ppm; space flow rate was; • oxygen influent concentration was 21%, and the effects of different operating parameters on incineration of isopropanol were tested. - The catalyst activity was tested by varying the influent isopropanol concentration and the results are shown in FIG. Figure 12 shows the effect of different influent concentrations on conversion. The test concentrations were 2,5G() ppm, 15G()ppm, 丨, 2(9) ppm, 9(10) ppm, and ppm; where τ50 was 239, respectively. (:, 239〇c, 247〇c, 253〇c, 248〇c; and Τ95 are 329〇C, 351γ, 395〇c, 4〇7〇c, 4l6〇c, respectively; The conversion efficiency of the influent concentration is better. From the perspective of heat balance, the high concentration of isopropanol also provides a relatively high calorific value, so the additional calorific value required for burning exhaust gas is relatively low; From the point of view of derivation, when the reaction is a non-zero-order positive-order reaction, the reaction rate is proportional to the concentration of the reactant, and the higher the reaction order, the more the reaction efficiency is 2. Therefore, the copper-cobalt heat storage stone catalyst In the near-current concentration range of 6〇〇 to 2,5〇() ppm, the conversion efficiency of the concentration of isopropanol in Vietnam is better. Figure 13 shows the effect of the spatial flow rate on the conversion of isopropanol. It can be seen that the reciprocal of the work/claw speed is the dwell time, and it can also indicate the stay.

O:\103\103498.DOC -20- 1293036 The shorter the time, the lower the conversion rate, and the longer the residence time of the general reactants in the reactor will contribute to the reaction. It can be seen from the figure that as the spatial flow rate increases, the conversion rate of isopropanol becomes lower and lower. The reaction temperature was 350. For example, when the space velocity is 13,500 hr-1, the conversion rate is 95%. When the space velocity is reduced to 6,75 0 hr·1, the conversion rate is increased to 99%; and when the space velocity is increased to 18,500. In hrel, the conversion rate is reduced to 94.6%, so from the above-data, the conversion rate does increase with the decrease of the space velocity, because the space velocity is reduced, so that the isopropanol is in the reactor. The prolonged residence time allowed the effective reaction of isopropanol and catalyst to increase, and the relationship between the space flow rate and the residence time and conversion rate in this experiment is shown in Table 2 below. Table 2 :

Space flow rate 18500 (hr·1) 13500(^-1) 6750(hr") 3375(hr·1) Residence time 〇.195(sec) 〇.267(sec) 0.533(sec) 1.〇67(sec) T5〇265°C 242°C 232°C 236°C Τ95 351°C 350°C 309°C 294°C Figure 14 shows the effect of influent oxygen concentration on isopropanol conversion, influent concentration of isopropanol It is 1500 ppm. The experimental process is the experimental data obtained from the atmospheric (〇2) concentration of 21% and 3〇0/. and 40%. It can be seen from the figure that as the oxygen concentration increases, the conversion rate also increases, but it increases. The trend is most obvious between the operating temperature range of 200 ° C and 400 ° C. With the increase of oxygen concentration (21 to 4 %), the conversion rate is improved. Taking 250 ° C as an example, 21%, 30 The conversion rate of % and 40% oxygen is 57%, 65%, 77%, so the change of oxygen concentration is helpful to the influence of copper-cobalt catalyst incineration of isopropanol. Since isopropanol must react with oxygen adsorbed on the catalyst, the oxygen O:\103\lO3498.DOC -21-1293036 degree is the trend of the higher conversion of isopropyl alcohol, and the results are shown in Table 3 below. Table 3: ', inlet oxygen concentration 21% 3 0% ------ 40% T50 242°C 235°C ------ 227°C T95 350°C 329°C 3ll°C ~^~ Example 5: Catalyst long-term decay test The increase in degree makes the collision probability of isopropyl alcohol and oxygen increase, so aerobic: 曲 • This experiment is to place the copper-cobalt heat storage stone catalyst (c'c〇=6:4) with a metal loading of 10% at high temperature. In the reactor, and control the operating conditions for the inflow - isopropyl alcohol concentration 1500ppm and space flow rate of 13500 hr.1, respectively, w,: 1 coffee C for 72 hours continuous test; and at any time =;; = The concentration of isopropyl alcohol is kept constant. ' The main purpose of the catalyst decay test is to observe whether the catalyst of the present invention may cause poisoning, scaling, breakage, and disappearance of active ingredients, and improve the production of the catalyst or It is to improve the application or pre-I. It can be seen from Figure 15 that this regenerative copper-cobalt catalyst stone is continuously tested at 300 °C and 350 °C for 72 hours, and the continuous test conversion of 3GG °C The rate was maintained. The conversion rate of the continuous test was maintained at 93% to 95〇/〇, and the conversion rate was maintained at a steady state. After the catalyst incineration equipment was evaluated, there was no obvious activity decay. - Via scanning electron microscopy (SEM), Figure 2a and the holes were respectively unreacted regenerative copper recording media and after 72 hours. Regenerative copper recording medium after time decay test, observed by scanning electron microscope

O:\103\103498.DOC 8 •22- 1293036 The catalyst surface is imaged at a magnification of 3 times. In comparison with the two figures, it is found that the surface of the catalyst exhibits a complete granular structure, and no broken particles or toxic substances and carbon deposits are found; it can be indirectly determined that the activity before and after the decay of the catalyst is not too Great change differences. Through the surface-by-element analysis (EDS), Figure 3 & and the figure ride are respectively unreacted regenerative copper-cobalt catalyst and a 72-hour long-term decay test • Regenerative copper-cobalt catalyst through the surface The values and maps presented by the elemental analysis map. The surface element analyzer and the scanning electron microscope analyzer are connected in series to show the relative intensity of the analytical element content, which is a semi-quantitative analysis. From the EDS values and spectra, it can be observed that the theoretical ratio of CuCo metal is 60: 40; and the actual EDS values are shown as 68 · · 32 and 6 〇: %, respectively, which indicates that it is possible to process the metal in the program. The distribution is still not uniform enough; it is also possible that this EDS elemental analysis is one of the many catalyst particles selected for analysis, so there is an error. In other elements, there is a considerable proportion of Ca and other metals, which is estimated to be the main component of the stone, which makes the carrier itself likely to have a comparable catalytic effect. The above-described embodiments are merely illustrative of the principles and effects of the invention and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a sinter reaction apparatus of the present invention. Fig. 2 is a scanning electron microscope analysis image of a copper-cobalt catalyst, magnified by O:\103\103498.DOC-23-(S) 1293036 at a rate of 3000 times; Figure 2a is freshly prepared; Figure 2b is used after 72 hours. Figure 3 is an EDS surface element analysis diagram of the copper catalyst; Figure 3a is freshly prepared; Figure 3b is used after 72 hours. Figure 4 is a diagram of the reaction system of the catalyst. Figure 5 is a schematic diagram of the filling mode of the catalytic reactor. Figure 6 shows the blank test, the carrier blank test (St〇ne), and 1〇0/. Copper-cobalt (weight ratio 6 · 4) catalyst (Cu / Co catalyst) at different temperatures vs. isopropanol | conversion ratio comparison chart. Figure 7 shows the effect of a catalyst with a metal loading of 3% on the conversion of isopropanol at different temperatures. Figure 8 shows the effect of a catalyst with a metal loading of 5% on the conversion of isopropanol at different temperatures. Figure 9 shows the effect of a catalyst with a metal loading of 〇1〇% on the conversion of isopropanol at different temperatures. Figure 10 shows the effect of different loadings and different metal catalysts on the conversion of isopropanol at different temperatures. Figure 11 shows the product selectivity of a copper-cobalt catalyst (Cu:c〇=6:4) with a metal loading of 10%. Figure 12 shows the effect of different influent concentrations on the conversion of isopropanol. Figure 13 shows the effect of different spatial flow rates on the conversion of isopropanol. Figure 14 shows the effect of different influent oxygen concentrations on the conversion of isopropanol. Figure 15 is a comparison of the long-term test of steel catalyst activity at different temperatures. [Main component symbol description] O:\103\103498.DOC -24- 1293036 101 Quartz sintered tube 102 Quartz sand 103 Quartz porous separator 104 Catalyst to be sintered 105 K-type thermocouple meter 106 Heating furnace 107 Refractory mud seal Cover 108 Exhaust gas outlet 109 Float flowmeter 110 Temperature controller 401 Air compressor 402 Oxygen cylinder 403 Nitrogen cylinder 404 Flowmeter 405 Volatile organic gas 406 Ball valve 407 Buffer tank 408 Catalyst bed 409 Tubular furnace 410 Thermostat 411 Discharge port 412 exhaust pipe head 413 needle valve 414 sampling port

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1293036

415 GC-FID 51 K-Type Thermometer 52 Catalyst Bed 53 Stainless Steel Net 54 Quartz Cotton

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Claims (1)

1293036 X. Patent application scope: 1 · A catalyst comprising: an active center comprising copper metal or steel oxide and a carrier for attaching the active center, and having the following characteristics: (1) heat resistance 100 To l〇〇〇°c; (II) specific heat is from 750 to 950 J/kg-°C; (III) The thermal conductivity is from 1 to 3 W/m-°C; (lv) the surface area of the particles is from 3 to 7 cm2; (v) the specific surface area is from 400 to 700 ηΓ1; and (vi) the filled porosity is From 〇·2 to 〇.6. The catalyst is from 0.005 2. According to the request, the average particle size of the carrier is 0.03 m 〇 3 · According to the catalyst of claim 1, 2800 Kg/m3 0 4 · According to the catalyst of the clear item 1, 0.8 〇 wherein the average density of the carrier is from 2500 to the particle sphericity of the carrier is self-producing. 5 5. The catalyst according to claim i, wherein the carrier is an inert material. 6. According to the request item! The catalyst, wherein the carrier is a heat storage stone. 7· f According to the catalyst of claim 1, wherein the ratio of copper metal and steel oxide to the catalyst is 1 to 30%. 8. According to the catalyst of μ, the ratio of copper metal and copper oxide to the catalyst is 3 to 1 〇〇/. . 9. The catalyst according to claim 1, wherein the active center further comprises a cobalt metal or a cobalt oxide. O:\103\103498.DOC 1293036 i. The catalyst according to claim 9, wherein the ratio of the weight of the cobalt metal and the cobalt oxide to the catalyst is from 1 to 30%. According to the catalyst of claim 10, the weight ratio of the cobalt metal and the cobalt oxide to the catalyst is 3 to 1 Torr. . 12. The catalyst according to claim 9, wherein the molar ratio of copper metal or copper oxide to cobalt metal or alkali oxide is from 9:1 to 5:5. 13. A method of manufacturing a catalyst according to any one of claims 1 to 12, the method comprising the steps of: (a) providing the carrier; (b) providing a solution containing copper metal or copper oxide; (4) The carrier is impregnated with a solution containing a copper metal or a copper oxide; (d) drying the product obtained in the step (c); and (e) calcining the product obtained from (d) to obtain the catalyst. 14. According to the method of claim 13, i. The octadecyl/cylinder (3) additionally comprises pickling and/or caustic washing of the carrier. 15: According to the method of claim 13, 1 in step + (b), step (b) further comprises providing a solution containing a cobalt metal or a ruthenium oxide; and the step ^ ^ ^ 乂 ^ (C) further comprising the carrier and the inclusion The metal or cobalt oxide solution is mixed and impregnated. 16. The method according to claim 13, wherein the solution containing only ^ ^ Θ % is a copper nitrate solution. There is a solution of @金属为续酸铭 17 · According to the method of claim 13 solution. 18. Dry at the temperature according to the method of claim 13. The drying in the step (4) is carried out at 80 to 120 ° C. O:\103\103498.DOC -2- 1293036 19. The method according to claim 18, wherein the drying of the step (4) lasts for more than 8 hours. 20. The method according to claim 13, wherein the step (4) is carried out under an inert atmosphere. Λ 21. According to the method of claim 13, the mother-in-law system is heated up to 82 to 9 and said to be burnt for more than 4 hours. 22. A method of treating volatile organic compounds using a catalyst according to any one of the claims. 23. The method of claim 22, wherein the volatile organic compound is isopropanol. 24. The method according to claim 22, which is carried out by a catalyst incineration method. 25. According to the method of claim 24, it is carried out by a regenerative catalyst incineration process. 26. The method of claim 22, wherein the processing temperature is from i 〇〇 to 1 〇〇. 27. The method of claim 26, wherein the processing temperature is 25 () to. 28. According to the branch of claim 22, the influent concentration of the volatile organic compounds in the towel is 100 to 5, 〇〇〇 ppm. 29. The method of claim 28 wherein the influent concentration of volatile organic compounds is from 600 to 2,500 ρρηι. 30. According to the request item 22$^, j., the oxygen influx concentration of the treatment is 2〇 to 50% 〇3 1 · According to the method of claim 3, the method, wherein the oxygen is treated The inflow concentration is 30 to 40 〇 / 〇〇 32. According to the method of claim 22, 1 ^ 嗖 2, wherein the spatial velocity of the treatment is 2, 〇〇〇 to 20.000 hr·1 〇 3 3 · upon request The method of Item 3 2, i ^ Bay 2, wherein the spatial velocity of the treatment is 3, 〇〇〇 to 7.000 hr-1. O:\103\103498.DOC