JP6980743B2 - Manufacturing method of catalyst used for haze reduction work - Google Patents

Description

The present invention relates to the field of catalyst technology, and specifically relates to a method for producing a catalyst used for haze reduction work.

Smoke causes severe harm to human health and the ecological environment. There is no much more effective measure and solution for the haze control surface. Methods such as vehicle traffic regulation, sprinkling injection, installation of air purifiers and suspension of factory operations due to long holidays can reduce air pollution locally, but cannot fundamentally solve the haze problem and require a large amount of water resources. Causes waste and increased electricity load. Over the last few years, the state has strengthened the input intensity of the appropriate smoke control surface at the government level, and the China Meteorological Bureau has printed and distributed "Implementing the" Air Pollution Control Action Plan "Implementation Plan". Among them, the artificial rainfall method is considered to be the most effective technology that has the potential to solve the haze problem.

Currently, under normal circumstances, the catalysts used in the artificial rainfall method are divided into three categories. The first type is a crystal nucleating agent such as silver iodide capable of producing a large amount of condensed nuclei or condensed nuclei; the second type is a refrigerant such as dry ice capable of forming a large amount of ice crystals with the moisture in the cloud. There is; the third kind is a hygroscopic agent such as salt particles that adsorbs water in clouds to form relatively large water droplets. Smoke is frequent in a cloudy or cloudy warm cloud environment. It is almost cloudy foggy weather under warm cloud weather environment, the intensity of solar radiation is weak, atmospheric convection activity is reduced, and the frequency of inversion is high, so the weather is always quiet and stable in the area. This puts the atmospheric layer in a stable state, which is detrimental to the diffusion of air pollutants and produces fumes. The artificial rainfall method can reduce PM2.5 by relying on the moisture settling action, but when the wind speed is low and the humidity is high, the effect of the artificial rainfall method on the PM2.5 concentration is not significant. Moreover, cold cloud catalysts for haze reduction (eg silver iodide, etc.) used in traditional artificial rainfall methods have a condensing effect only on water vapor and are fine particulate matter such as PM2.5. On the other hand, it does not have a clear adsorption action. With this, if only the traditional artificial rainfall method is relied on, the ideal effect on the haze extinction cannot be achieved, and the haze problem cannot be fundamentally solved. Therefore, by developing a catalyst for the fumes contaminants, under heavy pollution weather environment, conduct effective fumes cutting Gensaku industry, to be able to improve the air quality.

The technical problem to be solved by the present invention is to provide a method for producing a catalyst used for haze reduction work, in response to the above-mentioned shortcomings of the existing technology. The catalyst component of the present invention contains anhydrous calcium salt, sodium salt, magnesium salt and ammonium salt having hygroscopicity and cooling performance, which have strong hygroscopicity, and the average particle size is within 10 μm, so that the catalyst component has strong hygroscopicity and remarkable. It has a temperature lowering effect, has a relatively large adsorption area, has a good adsorption effect and a high adsorption rate for smoke pollutant granules in the air, and after forming the adsorption granules and undergoing natural sedimentation, Realized smoke reduction work.

In order to solve the above technical problems, the present invention adopts the following technical proposals. A method for manufacturing a catalyst used for haze reduction work having the following characteristics. The catalyst is a complex salt of Ca, Na, Mg and ammonium, and the molar ratio of Ca, Na, Mg and ammonium in the catalyst is 1: (0.2 to 0.5) :( 0.2 to 0.5) :( 0.5 to 0.8). ); The production process of the catalyst is as follows, that is, the average particle size is obtained by dissolving Ca salt, Na salt, Mg salt and ammonium salt in an organic solvent to form a slurry, and then spray-drying. To obtain a catalyst in which is within 10 μm.

The catalyst produced by the production method of the present invention is a composite salt of Ca, Na, Mg and ammonium, in which the anhydrous calcium salt, sodium salt and magnesium salt components have strong hygroscopicity, and when exposed to air, A high-speed moisture absorption function can be realized. Among them, the ammonium salt has hygroscopicity and at the same time absorbs heat during the dilution process and has a cooling effect. Therefore, the catalyst produced by the production method of the present invention has strong hygroscopicity and a remarkable cooling effect. Moreover, since the average particle size is within 10 μm, the adsorption area is relatively large, and the adsorption rate is high, the catalyst can quickly absorb water vapor and droplets in the air after sprinkling, and further, smoke pollutant granules in the air. Can be adsorbed. At the same time, the cooling effect of the catalyst can increase the relative saturated vapor pressure on the surface of the droplets to help the moisture absorption process, thus promoting the adsorption action on the fumes pollutant granules in the air and adsorbing them. After forming the granules, the adsorbed granules became large, and then naturally settled, the manual work of reducing smoke was realized. Furthermore, since the environmental impact of the catalyst in the production method of the present invention is small, secondary environmental pollution is not formed.

The present invention is a method for producing the catalyst, which has the following characteristics and is used for a haze reduction operation. The molar ratio of Ca, Na, Mg and ammonium in the catalyst is 1: (0.2 to 0.3) :( 0.3 to 0.4) :( 0.7 to 0.8). The catalyst composed of the mixing ratio has strong hygroscopicity and a remarkable cooling effect.

The present invention is a method for producing a catalyst used in a haze reduction operation, wherein the spray drying method is negative pressure spray drying. Preferably, the catalyst is made by a negative pressure spray drying method, which helps to evaporate the water content in the slurry and by controlling the spray drying rate, the catalyst having an average particle size of 10 μm or less. Obtainable.

The present invention is a method for producing the catalyst, which has the following characteristics and is used for a haze reduction operation. In the negative pressure spray drying process, the slurry can be ejected into a negative pressure environment by a high pressure rotary nozzle to perform granulation. By adopting a high-pressure rotary nozzle, the particle size of the catalyst can be controlled because it helps to disperse the slurry.

The present invention is a method for producing the catalyst, which has the following characteristics and is used for a haze reduction operation. The Ca salt is calcium nitrate, calcium chloride or calcium sulfate, the Na salt is sodium nitrate, sodium chloride or sodium sulfate, the Mg salt is magnesium nitrate, magnesium chloride or magnesium sulfate, and the ammonium salt is ammonium nitrate. , Ammonium chloride or magnesium sulfate. The Ca salt, Na salt, Mg salt and ammonium salt used as catalyst production raw materials of the present invention have a wide source and have a small environmental impact, and are therefore convenient for catalyst production.

The present invention is a method for producing the catalyst, which has the following characteristics and is used for a haze reduction operation. The Ca salt is calcium nitrate, the Na salt is sodium chloride, the Mg salt is magnesium nitrate, and the ammonium salt is ammonium nitrate. The catalyst produced at the above mixing ratio has strong hygroscopicity and a remarkable cooling effect.

The present invention is a method for producing the catalyst, which has the following characteristics and is used for a haze reduction operation. The organic solvent is a mixed solvent composed of methanol, ethanol and acetone, or a mixed solvent composed of methanol and acetone, or a mixed solvent composed of ethanol and acetone. By adopting the organic solvent composed of the above, various salt solutes in the catalyst manufacturing raw material can be well dissolved.

The present invention is a method for producing the catalyst, which has the following characteristics and is used for a haze reduction operation. The organic solvent is a mixed solvent in which ethanol and acetone are mixed at a mass ratio of 1: (0.9-1). By adopting the organic solvent composed of the above, all the various salts in the catalyst manufacturing raw material have good dissolution performance.

The present invention has the following advantages over existing techniques.

1. 1. The catalyst component in the production method of the present invention contains an anhydrous calcium salt, a sodium salt, a magnesium salt and an ammonium salt having hygroscopicity and cooling performance, and has an average particle size of 10 μm or less. The catalyst produced by the production method of the present invention has strong hygroscopicity and remarkable cooling action, has a relatively large adsorption area, and has a good adsorption effect and a high adsorption rate for fumes pollutant granules in the air. After forming adsorption granules and undergoing natural sedimentation, smoke reduction work is realized. At the same time, the cooling effect of the catalyst improves the adsorption action, forms the relative saturated vapor pressure on the droplet surface, and promotes the moisture absorption process, further improving the adsorption action of the catalyst on the fumes pollutant granules. matter.

2. Since the environmental impact of the catalyst in the production method of the present invention is small, no secondary environmental pollution is formed.

3. 3. The catalyst manufacturing process of the present invention is comparatively easy, has a two-step process of dissolving salt substances and spray drying, and is a common process technology that is common to all, has a low degree of difficulty in implementation, and is convenient for industrial expansion. ..

Four. Since the organic solvent used in the present invention is convenient for recovery and utilization, waste of resources should be reduced.

Next, an embodiment of the present invention will be further described.

Embodiment 1

The catalyst of the first embodiment is a composite salt of Ca, Na, Mg and ammonium, and the molar ratio of Ca, Na, Mg and ammonium in the catalyst is 1: 0.2: 0.4: 0.8, and the catalyst manufacturing process. Is as follows. 164.0 g of anhydrous calcium nitrate, 11.7 g of sodium chloride, 59.2 g of anhydrous magnesium nitrate and 64.0 g of ammonium nitrate are dissolved in 3 L of organic solvent to form a slurry , and then negative pressure spraying is applied to the slurry with a high-pressure rotary nozzle. Drying was performed to produce a catalyst. The organic solvent is a mixed solvent in which ethanol and acetone are mixed at a mass ratio of 1: 0.9.

As a result of dispersing the catalyst of the present embodiment 1 in n-hexane and detecting it with a laser particle size meter, the average particle size of the catalyst of the present embodiment 1 is 8.6 μm.

The Ca salt in the first embodiment may be calcium chloride or calcium sulfate, the Na salt may be sodium nitrate or sodium sulfate, the Mg salt may be magnesium chloride or magnesium sulfate, and the ammonium salt may be. It may be ammonium chloride or ammonium sulfate.

Embodiment 2

The catalyst of the second embodiment is a composite salt of Ca, Na, Mg and ammonium, and the molar ratio of Ca, Na, Mg and ammonium in the catalyst is 1: 0.3: 0.3: 0.8, and the catalyst manufacturing process. Is as follows. Anhydrous calcium nitrate 164.0 g, sodium chloride 17.5 g, after forming a slurry by dissolving anhydrous magnesium nitrate 44.4g ammonium nitrate 64.0g organic solvent 3L, a high pressure rotary nozzle for slurry, shade atomizer drying Was performed to produce a catalyst. The organic solvent is a mixed solvent in which ethanol and acetone are mixed at a mass ratio of 1: 0.95.

As a result of dispersing the catalyst of the present embodiment 2 in n-hexane and detecting it with a laser particle size meter, the average particle size of the catalyst of the present embodiment 2 is 7.9 μm.

The Ca salt in the second embodiment may be calcium chloride or calcium sulfate, the Na salt may be sodium nitrate or sodium sulfate, the Mg salt may be magnesium chloride or magnesium sulfate, and the ammonium salt may be. It may be ammonium chloride or ammonium sulfate.

Embodiment 3

The catalyst of the third embodiment is a composite salt of Ca, Na, Mg and ammonium, and the molar ratio of Ca, Na, Mg and ammonium in the catalyst is 1: 0.2: 0.4: 0.7, and the catalyst manufacturing process. Is as follows. Anhydrous calcium nitrate 164.0 g, sodium chloride 11.7 g, after forming a slurry by dissolving anhydrous magnesium nitrate 59.2g ammonium nitrate 56.0g organic solvent 3L, a high pressure rotary nozzle for slurry, shade atomizer drying Was performed to produce a catalyst. The organic solvent is a mixed solvent in which ethanol and acetone are mixed at a mass ratio of 1: 1.

As a result of dispersing the catalyst of the present embodiment 3 in n-hexane and detecting it with a laser particle size meter, the average particle size of the catalyst of the present embodiment 3 is 7.3 μm.

The Ca salt in the third embodiment may be calcium chloride or calcium sulfate, the Na salt may be sodium nitrate or sodium sulfate, the Mg salt may be magnesium chloride or magnesium sulfate, and the ammonium salt may be. It may be ammonium chloride or ammonium sulfate.

Embodiment 4

The catalyst of the fourth embodiment is a composite salt of Ca, Na, Mg and ammonium, and the molar ratio of Ca, Na, Mg and ammonium in the catalyst is 1: 0.5: 0.4: 0.8, and the catalyst manufacturing process. Is as follows. Anhydrous calcium nitrate 164.0 g, sodium chloride 29.2 g, after forming a slurry by dissolving anhydrous magnesium nitrate 59.2g ammonium nitrate 64.0g organic solvent 4L, a high pressure rotary nozzle for slurry, shade atomizer drying Was performed to produce a catalyst. The organic solvent is a mixed solvent in which ethanol and acetone are mixed at a mass ratio of 1: 1.

As a result of dispersing the catalyst of the present embodiment 4 in n-hexane and detecting it with a laser particle size meter, the average particle size of the catalyst of the present embodiment 4 is 5.1 μm.

The Ca salt in the fourth embodiment may be calcium chloride or calcium sulfate, the Na salt may be sodium nitrate or sodium sulfate, the Mg salt may be magnesium chloride or magnesium sulfate, and the ammonium salt may be. It may be ammonium chloride or ammonium sulfate.

Embodiment 5

The catalyst of the fifth embodiment is a composite salt of Ca, Na, Mg and ammonium, and the molar ratio of Ca, Na, Mg and ammonium in the catalyst is 1: 0.26: 0.5: 0.75. Is as follows. After dissolving 164.0 g of anhydrous calcium nitrate, 15.2 g of sodium chloride, 74.0 g of anhydrous magnesium nitrate and 60.0 g of ammonium nitrate in 2.5 L of organic solvent to form a slurry , a negative pressure spray is applied to the slurry with a high-pressure rotary nozzle. Drying was performed to produce a catalyst. The organic solvent is a mixed solvent in which ethanol and acetone are mixed at a mass ratio of 1: 1.

As a result of dispersing the catalyst of the present embodiment 5 in n-hexane and detecting it with a laser particle size meter, the average particle size of the catalyst of the present embodiment 5 is 9.9 μm.

The Ca salt in the fifth embodiment may be calcium chloride or calcium sulfate, the Na salt may be sodium nitrate or sodium sulfate, the Mg salt may be magnesium chloride or magnesium sulfate, and the ammonium salt may be. It may be ammonium chloride or ammonium sulfate.

Embodiment 6

The catalyst of the sixth embodiment is a composite salt of Ca, Na, Mg and ammonium, and the molar ratio of Ca, Na, Mg and ammonium in the catalyst is 1: 0.3: 0.34: 0.75. Is as follows. Anhydrous calcium nitrate 164.0 g, sodium chloride 17.5 g, after forming a slurry by dissolving anhydrous magnesium nitrate 50.3g ammonium nitrate 60g in an organic solvent 2.5L, a high pressure rotary nozzle for slurry, shade atomizer drying Was performed to produce a catalyst. The organic solvent is a mixed solvent in which ethanol and acetone are mixed at a mass ratio of 1: 1.

As a result of dispersing the catalyst of the present embodiment 6 in n-hexane and detecting it with a laser particle size meter, the average particle size of the catalyst of the present embodiment 6 is 9.7 μm.

The Ca salt in the sixth embodiment may be calcium chloride or calcium sulfate, the Na salt may be sodium nitrate or sodium sulfate, the Mg salt may be magnesium chloride or magnesium sulfate, and the ammonium salt may be. It may be ammonium chloride or ammonium sulfate.

Embodiment 7

The catalyst of the seventh embodiment is a composite salt of Ca, Na, Mg and ammonium, and the molar ratio of Ca, Na, Mg and ammonium in the catalyst is 1: 0.26: 0.34: 0.75. Is as follows. Anhydrous calcium nitrate 164.0 g, sodium chloride 15.2 g, after forming a slurry by dissolving anhydrous magnesium nitrate 50.3g ammonium nitrate 60g in an organic solvent 3.5 L, a high pressure rotary nozzle for slurry, shade atomizer drying Was performed to produce a catalyst. The organic solvent is a mixed solvent in which methanol and acetone are mixed at a mass ratio of 1: 1.

As a result of dispersing the catalyst of the present embodiment 7 in n-hexane and detecting it with a laser particle size meter, the average particle size of the catalyst of the present embodiment 7 is 7.2 μm.

The Ca salt in the seventh embodiment may be calcium chloride or calcium sulfate, the Na salt may be sodium nitrate or sodium sulfate, the Mg salt may be magnesium chloride or magnesium sulfate, and the ammonium salt may be. It may be ammonium chloride or ammonium sulfate.

8th embodiment

The catalyst of the present embodiment 8 is a composite salt of Ca, Na, Mg and ammonium, and the molar ratio of Ca, Na, Mg and ammonium in the catalyst is 1: 0.24: 0.38: 0.78, and the catalyst manufacturing process. Is as follows. After dissolving 111.0 g of calcium chloride, 14.0 g of sodium chloride, 56.2 g of anhydrous magnesium nitrate and 62.4 g of ammonium nitrate in 3.7 L of organic solvent to form a slurry , use a high-pressure rotary nozzle to spray dry the slurry under negative pressure. I went and made a catalyst. The organic solvent is a mixed solvent in which methanol, methanol and acetone are mixed at a mass ratio of 0.5: 0.5: 1.

As a result of dispersing the catalyst of the present embodiment 8 in n-hexane and detecting it with a laser particle size meter, the average particle size of the catalyst of the present embodiment 8 is 7.7 μm.

The Ca salt in the eighth embodiment may be calcium nitrate or calcium sulfate, the Na salt may be sodium nitrate or sodium sulfate, the Mg salt may be magnesium chloride or magnesium sulfate, and the ammonium salt may be. It may be ammonium chloride or ammonium sulfate.

Embodiment 9

The catalyst of the present embodiment 9 is a composite salt of Ca, Na, Mg and ammonium, and the molar ratio of Ca, Na, Mg and ammonium in the catalyst is 1: 0.24: 0.2: 0.5, and the catalyst manufacturing process. Is as follows. Dissolve 111.0 g of anhydrous calcium chloride, 14.0 g of sodium chloride, 29.6 g of anhydrous magnesium nitrate and 40 g of ammonium nitrate in 3.7 L of organic solvent to form a slurry , and then use a high-pressure rotary nozzle to spray dry the slurry with negative pressure. Was performed to produce a catalyst. The organic solvent is a mixed solvent in which methanol, methanol and acetone are mixed at a mass ratio of 0.5: 0.5: 1.

As a result of dispersing the catalyst of the present embodiment 9 in n-hexane and detecting it with a laser particle size meter, the average particle size of the catalyst of the present embodiment is 7.5 μm.

The Ca salt in the ninth embodiment may be calcium nitrate or calcium sulfate, the Na salt may be sodium nitrate or sodium sulfate, the Mg salt may be magnesium chloride or magnesium sulfate, and the ammonium salt may be. It may be ammonium chloride or ammonium sulfate.

After evaluating the smoke reduction effect of the catalyst of the first to fourth embodiments of the present invention and using the catalyst at different times by using the simulated artificial cloud chamber system, the environmental temperature change in the artificial cloud chamber system and PM2. Tables 1 to 4 show the results of determining the effect of the catalyst by calculating the removal efficiency of PM2.5 particulate matter by simulating with 5 indices (unit is μg / m ^3).

Among them, the calculation formula of elimination efficiency (%) is as follows.
Elimination efficiency (%) = (Initial PM2.5 index-PM2.5 index after catalyst use) / Initial PM2.5 index x 100%

As can be seen from Tables 1 to 4, by using the catalysts of the first to fourth embodiments of the present invention, the environmental temperature and the PM2.5 particulate matter content in the simulated artificial cloud chamber system can be reduced, and the PM2.5 particulate matter content can be reduced. As time increases, the environmental temperature and PM2.5 particulate matter content in the simulated artificial cloud chamber system decrease, and the removal efficiency improves. The catalysts of Embodiments 1 to 4 of the present invention have good cooling, PM2.5 particulate matter removal, and haze reduction effects on the environment. With the increase in time, the effects of cooling and haze reduction become remarkable. After the usage time reaches 2 hours, the effects of cooling and reducing smoke gradually become stable, and the removal efficiency of PM2.5 particulate matter by the catalyst in the present invention can reach 83% or more.

The contents described above are only preferred embodiments of the present invention, and are not any restrictions on the present invention. Any simple modifications, modifications and equivalent modifications made to the above embodiments based on the technical nature of the invention are all within the scope of the invention.

Claims (8)

It is a kind of catalyst, and the following matters, that is, the catalyst is a composite salt of Ca, Na, Mg and ammonium, and the molar ratio of Ca, Na, Mg and ammonium in the catalyst is 1: (0.2 to 0.5). ): (0.2 to 0.5): (0.5 to 0.8); The catalyst fabrication process is as follows: Ca salt, Na salt, Mg salt and ammonium salt are dissolved in an organic solvent to form a slurry. A method for producing a catalyst used in a smoke reduction operation, which comprises obtaining a catalyst having an average particle size of 10 μm or less by spray drying. The haze reduction according to claim 1, wherein the molar ratio of Ca, Na, Mg and ammonium in the catalyst is 1: (0.2 to 0.3) :( 0.3 to 0.4) :( 0.7 to 0.8). A method for manufacturing a catalyst used in work. The method for producing a catalyst used in the haze reduction work according to claim 1, wherein the spray drying method is negative pressure spray drying. The method for producing a catalyst used in the smoke reduction work according to claim 3, wherein in the negative pressure spray drying process, the slurry is ejected into a negative pressure environment to perform granulation with a high-pressure rotary nozzle. The Ca salt is calcium nitrate, calcium chloride or calcium sulfate, the Na salt is sodium nitrate, sodium chloride or sodium sulfate, the Mg salt is magnesium nitrate, magnesium chloride or magnesium sulfate, and the ammonium salt is ammonium nitrate. , The method for producing a catalyst used for the smoke reduction work according to claim 1, wherein it is ammonium chloride or magnesium sulfate. The catalyst used for the smoke reduction work according to claim 5, wherein the Ca salt is calcium nitrate, the Na salt is sodium chloride, the Mg salt is magnesium nitrate, and the ammonium salt is ammonium nitrate . Manufacturing method . The claim is characterized in that the organic solvent is a mixed solvent composed of methanol, ethanol and acetone, a mixed solvent composed of methanol and acetone, or a mixed solvent composed of ethanol and acetone. The method for producing a solvent used for the smoke reduction work according to 1. The method for producing a catalyst used in the haze reduction operation according to claim 7, wherein the organic solvent is a mixed solvent in which ethanol and acetone are mixed in a mass ratio of 1: (0.9-1).