CN114377654B - Ammonia adsorption material for reducing ammonia volatilization amount and liquid surface covering ball thereof - Google Patents
Ammonia adsorption material for reducing ammonia volatilization amount and liquid surface covering ball thereof Download PDFInfo
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Abstract
The invention discloses an ammonia adsorbing material for reducing ammonia volatilization and a liquid surface covering ball thereof, wherein the ammonia adsorbing material comprises the following components in parts by mass: 60-70 parts of modified coconut shell activated carbon, 15-20 parts of calcium superphosphate, 75-80 parts of zinc chloride, 3-8 parts of diatomite, 2-4 parts of sodium alginate and 90-100 parts of ZIF-8 crystal powder, and the preparation method comprises the following steps: s1, mixing treatment; s2, activating treatment; s3, modification treatment; and S4, coating. The liquid level covers the ball including the spheroid and the floater ring that the spheroid middle part overcoat was established, and first one of spheroid is the cavity, and the spheroid lower half is solid construction, and spheroid lower half center department is equipped with the mainboard, and the spheroid lower half symmetry of mainboard both sides is equipped with a plurality of flutings, is equipped with the spacer that the coating has ammonia adsorption material between the fluting. According to the invention, the modified coconut shell activated carbon and zinc chloride are activated to obtain mixed powder with strong adsorbability, and then the mixed powder is coated on ZIF-8 crystal powder to obtain an adsorption material with a rich pore structure and good ammonia adsorption performance.
Description
Technical Field
The invention relates to the technical field of ammonia adsorbing materials, in particular to an ammonia adsorbing material for reducing ammonia volatilization and a liquid surface covering ball thereof.
Background
Ammonia is a compound of nitrogen and hydrogen, formula NH 3 It is a common industrial raw material, which is a colorless gas at normal temperature, has strong pungent odor, is very easy to dissolve in water, can dissolve 700 times volume of ammonia at normal temperature and normal pressure by 1 volume of water, and the aqueous solution is called ammonia water. The liquid ammonia is a refrigerant. Ammonia is also an important raw material for manufacturing nitric acid, fertilizers and explosives, and plays an important role in agriculture, medicine and defense industry. Ammonia has a wide range of uses and is also corrosive, with ammonia being one of the most abundant inorganic compounds in the world, and more than eighty percent of ammonia being used in the manufacture of fertilizers. However, ammonia is also a toxic and harmful alkaline pollution source, and ammonia dissolved in the atmosphere and the ocean brings great inconvenience to the production and the life of people, and has seriously influenced the living environment of animals and plants in nature. Therefore, further research on ammonia purification and adsorption is required.
For the treatment of ammonia, firstly, strict control on the discharge capacity is required, and secondly, the biological method, the catalytic decomposition method and the adsorption method can effectively remove ammonia. The plant absorption and purification are the more popular topics in recent years, but the effect of substance purification and absorption is limited, so that the method is still in the initial research stage at present, most of indoor free ammonia is treated, and the purpose of industrial production cannot be achieved. The most widely used method is adsorption method, and chemical adsorption is used for adsorbing acidic groups or NH in material structure 3 The coordination effect is performed to form a relatively firm adsorption effect. The adsorbent material has various types and different adsorption efficiency, and a proper ammonia adsorbent is selected according to the requirement.
Patent CN104069790A discloses an ammonia adsorbent and a preparation method thereof, and adopts the following technical scheme: crushing the coal-fired furnace slag, taking a certain amount of furnace slag powder, adding 10-50% phosphoric acid solution, soaking for 3-24h at room temperature, and then drying. And (3) after drying, heating the solid matter from the room temperature to a preset temperature (300-700 ℃) and preserving heat for 2 hours, cooling to the room temperature, taking out the final product, washing the final product to be neutral by using distilled water, drying, and bottling for later use to obtain the ammonia gas adsorbent. Although the preparation method is simple, the cost is low, and the adsorption efficiency is certain, the effect is not good when a large amount of ammonia is adsorbed, and the concept of environmental protection is not met.
Disclosure of Invention
In view of the above problems, the present invention provides an ammonia adsorbent for reducing the amount of ammonia volatilized and a liquid surface covering sphere thereof.
The technical scheme of the invention is as follows:
an ammonia adsorbing material for reducing ammonia volatilization amount, which comprises the following components in parts by mass: 60-70 parts of modified coconut shell activated carbon, 15-20 parts of calcium superphosphate, 75-80 parts of zinc chloride, 3-8 parts of diatomite, 2-4 parts of sodium alginate and 90-100 parts of ZIF-8 crystal powder, and the preparation method of the ammonia adsorption material comprises the following steps:
s1, mixing treatment: zinc chloride is added into the mixture according to the mass ratio of 1:5, dissolving in water, stirring for 15min, adding modified coconut shell activated carbon, calcium superphosphate and diatomite, continuously stirring for 45min, standing for 8h, and drying at 120 ℃ for 2h to obtain mixed powder;
s2, activation treatment: placing the mixed powder in a vacuum oven, heating to 450-500 deg.C at a heating rate of 10 deg.C/min, maintaining for 4h, and naturally cooling to room temperature of 26-28 deg.C to obtain activated powder;
s3, modification treatment: activating powder according to the mass ratio of 1:8, dissolving in an oxalic acid solution with the mass concentration of 15-20%, standing and soaking for 30min, then washing for 3 times by using deionized water, wherein the pH value of a washing solution is 6.5-7, drying for 2h at the temperature of 80 ℃, adding sodium alginate powder, and shaking and mixing to obtain modified powder;
s4, coating treatment: mixing ZIF-8 crystal powder according to a mass ratio of 1:2, adding the modified powder, performing ultrasonic oscillation and mixing for 30min, then putting the mixture into a 220 ℃ oven, drying the excess water, and then preserving the heat for 3h to obtain dry ammonia adsorption material powder.
Further, the preparation method of the modified coconut shell activated carbon comprises the following steps: washing fresh coconut shell raw material with water content of 10-15% for 3 times, drying at 80 ℃ for 12h, crushing, sieving with a 60-80 mesh sieve, and then mixing the raw material with the powder according to a mass ratio of 1:15 in proportion, dissolving in an ethanol solution with the mass concentration of 70%, carrying out ultrasonic treatment for 1h, filtering to obtain a filter cake, evaporating and recovering the residual solution, drying the filter cake for 8h at the temperature of 75 ℃ to obtain modified coconut shell powder, heating the modified coconut shell powder for 6h at the temperature of 450 ℃ to obtain modified coconut shell activated carbon, and carrying out vacuum sealing storage. Can effectively improve the activity of the coconut shell, thereby improving the adsorptivity to ammonia.
Further, in the mixing treatment in the step S1, the calcium superphosphate and the diatomite are crushed and then pass through a 60-80 mesh screen, and the stirring speed is 50-60r/min. The uniform particle size is ensured, and the adsorption effect is improved.
Further, in the modification treatment in the step S3, the sodium alginate powder is crushed and then passed through a 60-80 mesh screen. The aim is that the sodium alginate powder has uniform particle size and is consistent with the activated powder.
Further, the preparation method of the ZIF-8 crystal powder in the coating treatment of step S4 is:
s4-1: zinc nitrate hexahydrate is mixed according to the mass ratio of 1:1 is dissolved in dimethyl imidazole with the concentration of 1.5mol/L, mixed and stood for 2 hours;
s4-2: mixing a benzimidazole solution and an N, N-dimethylformamide solution according to a mass ratio of 1:3, adding the mixed solution obtained in the step S4-1, stirring, mixing, centrifuging, separating supernatant and precipitate, washing the obtained precipitate with deionized water for 3 times, drying, and crushing the precipitate and sieving the precipitate with a 60-80-mesh sieve to obtain ZIF-8 crystal powder.
Further, in the step S4-2, the concentration of the benzimidazole solution is 0.8mol/L, the concentration of the N, N-dimethylformamide solution is 0.05mol/L, and the stirring speed is 50r/min. So that the prepared ZIF-8 crystal powder has good thermal stability and chemical stability.
Above-mentioned arbitrary one a liquid level that is used for reducing ammonia adsorption material of ammonia volume of volatilizing covers ball, including the spheroid and the showy ring that spheroid middle part overcoat was established, the first half of spheroid is the cavity, and the spheroid lower half is solid construction, and spheroid lower half center department is equipped with the mainboard, the spheroid lower half symmetry of mainboard both sides is equipped with a plurality of flutings, be equipped with the spacer that is coated with ammonia adsorption material between the fluting, with the spheroid lower half of spacer vertical direction is equipped with a plurality of through-holes, the through-hole runs through spheroid, mainboard and spacer, and the inside slide bar that is equipped with ammonia adsorption material and makes of through-hole, slide bar and mainboard sliding connection.
Furthermore, the sectional areas of the two ends of the sliding rod are larger than the sectional area of the middle part of the sliding rod, the middle part of the sliding rod is in sliding connection with the pore passage arranged on the main board, the position of the sliding rod close to the two ends of the sliding rod is provided with a limiting ring, and the area of the limiting ring is smaller than that of the through hole and larger than that of the pore passage. The sliding rod is used for preventing the sliding rod from falling out of the through hole, and can slide under the action of water flow to increase the adsorption area.
Furthermore, the spheres and the floating rings are made of polypropylene foam, the spheres are 4-6 in one group and are connected through polypropylene connecting rods, and sand grains used for polishing the sliding rods are filled in the main board. The sliding rod continuously keeps higher adsorption effect through the friction between the sand grains and the sliding rod.
The beneficial effects of the invention are:
(1) According to the ammonia adsorption material, the modified coconut shell activated carbon and zinc chloride are subjected to activation treatment to obtain mixed powder with strong adsorbability, after ethanol treatment, part of pectin and cocoanut glucoside of coconut shells are removed, so that the formation of a pore structure of the product activated carbon is facilitated, and then the product activated carbon is coated on ZIF-8 crystal powder to obtain the adsorption material with a rich pore structure and a large specific surface area, and the adsorption material is high in stability and has good ammonia adsorption performance.
(2) According to the ammonia adsorption material, the preparation method of the ZIF-8 crystal powder is improved, so that the ZIF-8 structure is not damaged, and the ZIF-8 crystal powder can be fused with the modified and activated mixed powder, is green and environment-friendly, and can be recycled.
(3) The liquid surface covering ball of the ammonia adsorbing material greatly improves the ammonia adsorbing effect in sewage by carrying the ammonia adsorbing material spacer and the sliding rod, can effectively inhibit the volatilization of ammonia, reduces the pollution to the atmosphere and water quality, and has compact structure, good stability and strong practicability.
Drawings
FIG. 1 is a schematic view of the overall structure of a liquid level covering sphere according to the present invention;
FIG. 2 is a front view of the level covering sphere of the present invention;
FIG. 3 is a side view of the liquid level covering sphere of the present invention;
FIG. 4 is a schematic view of the structure of the liquid level covering ball sliding rod of the present invention;
FIG. 5 is a schematic view showing a structure of a liquid surface covering ball group in embodiment 10 of the present invention;
FIG. 6 is a schematic view showing a structure of a liquid surface covering sphere group in embodiment 11 of the present invention;
fig. 7 is a schematic structural view of a liquid level covering ball group in embodiment 12 of the present invention.
Wherein, the device comprises a sphere 1, a floating ring 2, a main plate 3, a slot 4, a spacer 5, a through hole 6, a slide bar 7, a limiting ring 8 and a polypropylene connecting rod 9.
Detailed Description
Example 1
An ammonia adsorbing material for reducing ammonia volatilization amount, which comprises the following components in parts by mass: 65 parts of modified coconut shell activated carbon, 16 parts of calcium superphosphate, 78 parts of zinc chloride, 5 parts of diatomite, 3 parts of sodium alginate and 96 parts of ZIF-8 crystal powder, wherein the preparation method of the modified coconut shell activated carbon comprises the following steps: washing a fresh coconut shell raw material with the water content of 12% for 3 times, drying for 12 hours at the temperature of 80 ℃, crushing the raw material through a 70-mesh screen, and then mixing the raw material with the water content of 1:15 in a mass concentration of 70% in an ethanol solution, carrying out ultrasonic treatment for 1h, filtering to obtain a filter cake, evaporating and recovering the rest solution, drying the filter cake at 75 ℃ for 8h to obtain modified coconut shell powder, heating the modified coconut shell powder at 450 ℃ for 6h to obtain modified coconut shell activated carbon, and carrying out vacuum seal storage, wherein the preparation method of the ammonia adsorption material comprises the following steps:
s1, mixing treatment: zinc chloride is added into the mixture according to the mass ratio of 1:5, dissolving in water, stirring for 15min, adding modified coconut shell activated carbon, calcium superphosphate and diatomite, crushing the calcium superphosphate and the diatomite, sieving the crushed calcium superphosphate and the diatomite with a 70-mesh sieve, continuously stirring for 45min, standing for 8h at the stirring speed of 55r/min, and drying for 2h at 120 ℃ to obtain mixed powder;
s2, activation treatment: placing the mixed powder in a vacuum oven, heating to 460 ℃ at a heating rate of 10 ℃/min, preserving heat for 4h, and naturally cooling to 27 ℃ at room temperature to obtain activated powder;
s3, modification treatment: activating powder according to the mass ratio of 1: dissolving 8 in an oxalic acid solution with the mass concentration of 17%, standing and soaking for 30min, then washing for 3 times by using deionized water, wherein the pH value of a washing solution is 6.8, drying for 2h at 80 ℃, adding sodium alginate powder, crushing the sodium alginate powder, sieving by using a 70-mesh sieve, and shaking and mixing to obtain modified powder;
s4, coating treatment: mixing ZIF-8 crystal powder according to a mass ratio of 1:2, dissolving the mixture in deionized water, adding the modified powder, performing ultrasonic oscillation and mixing for 30min, then putting the mixture into a 220 ℃ oven, drying excessive water, and keeping the temperature for 3h to obtain dry ammonia adsorption material powder;
the preparation method of the ZIF-8 crystal powder comprises the following steps:
s4-1: zinc nitrate hexahydrate is mixed according to the mass ratio of 1:1 is dissolved in dimethyl imidazole with the concentration of 1.5mol/L, mixed and stood for 2 hours;
s4-2: mixing a benzimidazole solution and an N, N-dimethylformamide solution according to a mass ratio of 1:3, mixing, wherein the concentration of the benzimidazole solution is 0.8mol/L, the concentration of the N, N-dimethylformamide solution is 0.05mol/L, adding the mixed solution obtained in the step S4-1, stirring, mixing and centrifuging, wherein the stirring speed is 50r/min, separating supernate and precipitate, washing the obtained precipitate with deionized water for 3 times, drying and crushing the precipitate by using a 70-mesh screen to obtain ZIF-8 crystal powder.
Example 2
This embodiment is substantially the same as embodiment 1, except that: the ammonia adsorption material has different component mass ratios.
An ammonia adsorbing material for reducing ammonia volatilization amount, which comprises the following components in parts by mass: 60 parts of modified coconut shell activated carbon, 15 parts of calcium superphosphate, 75 parts of zinc chloride, 3 parts of diatomite, 2 parts of sodium alginate and 90 parts of ZIF-8 crystal powder.
Example 3
This embodiment is substantially the same as embodiment 1, except that: the ammonia adsorption material has different component mass ratios.
An ammonia adsorbing material for reducing ammonia volatilization amount, which comprises the following components in parts by mass: 70 parts of modified coconut shell activated carbon, 20 parts of calcium superphosphate, 80 parts of zinc chloride, 8 parts of diatomite, 4 parts of sodium alginate and 100 parts of ZIF-8 crystal powder.
Example 4
This embodiment is substantially the same as embodiment 1, except that: the modified coconut shell activated carbon has different preparation method parameters.
The preparation method of the modified coconut shell activated carbon comprises the following steps: washing fresh coconut shell raw material with water content of 10% for 3 times, drying at 80 ℃ for 12h, crushing and screening by a 60-mesh screen, and then, mixing the raw material with the raw material according to a mass ratio of 1:15 in the weight ratio, dissolving in an ethanol solution with the mass concentration of 70%, carrying out ultrasonic treatment for 1h, filtering to obtain a filter cake, evaporating and recovering the residual solution, drying the filter cake for 8h at the temperature of 75 ℃ to obtain modified coconut shell powder, heating the modified coconut shell powder for 6h at the temperature of 450 ℃ to obtain modified coconut shell activated carbon, and carrying out vacuum sealing storage.
Example 5
This embodiment is substantially the same as embodiment 1, except that: the modified coconut shell activated carbon has different preparation method parameters.
The preparation method of the modified coconut shell activated carbon comprises the following steps: washing fresh coconut shell raw materials with the water content of 15% for 3 times, drying for 12 hours at the temperature of 80 ℃, crushing through a 80-mesh screen, and then mixing according to the mass ratio of 1:15 in the weight ratio, dissolving in an ethanol solution with the mass concentration of 70%, carrying out ultrasonic treatment for 1h, filtering to obtain a filter cake, evaporating and recovering the residual solution, drying the filter cake for 8h at the temperature of 75 ℃ to obtain modified coconut shell powder, heating the modified coconut shell powder for 6h at the temperature of 450 ℃ to obtain modified coconut shell activated carbon, and carrying out vacuum sealing storage.
Example 6
This embodiment is substantially the same as embodiment 1, except that: the preparation method parameters of the ammonia adsorption material are different.
The preparation method of the ammonia adsorption material comprises the following steps:
s1, mixing treatment: zinc chloride is added into the mixture according to the mass ratio of 1:5, dissolving in water, stirring for 15min, adding modified coconut shell activated carbon, calcium superphosphate and diatomite, crushing the calcium superphosphate and the diatomite, sieving the crushed calcium superphosphate and the diatomite with a 60-mesh sieve, continuously stirring for 45min, standing for 8h at the stirring speed of 50r/min, and drying for 2h at 120 ℃ to obtain mixed powder;
s2, activation treatment: placing the mixed powder in a vacuum oven, heating to 450 ℃ at a heating rate of 10 ℃/min, preserving heat for 4h, and naturally cooling to room temperature of 26 ℃ to obtain activated powder;
s3, modification treatment: activating powder according to the mass ratio of 1: dissolving 8 in oxalic acid solution with the mass concentration of 15%, standing and soaking for 30min, then washing for 3 times by using deionized water, wherein the pH value of a washing solution is 6.5, drying for 2h at the temperature of 80 ℃, adding sodium alginate powder, crushing the sodium alginate powder, sieving by using a 60-mesh sieve, and shaking and mixing to obtain modified powder;
s4, coating treatment: mixing ZIF-8 crystal powder according to a mass ratio of 1:2, adding the modified powder, performing ultrasonic oscillation and mixing for 30min, then putting the mixture into a 220 ℃ oven, drying the excess water, and then preserving the heat for 3h to obtain dry ammonia adsorption material powder.
Example 7
This embodiment is substantially the same as embodiment 1, except that: the preparation method parameters of the ammonia adsorption material are different.
The preparation method of the ammonia adsorption material comprises the following steps:
s1, mixing treatment: zinc chloride is added into the mixture according to the mass ratio of 1:5, dissolving in water, stirring for 15min, adding modified coconut shell activated carbon, calcium superphosphate and kieselguhr, crushing the calcium superphosphate and the kieselguhr, sieving by a 80-mesh sieve, continuously stirring for 45min, standing for 8h at the stirring speed of 60r/min, and drying for 2h at 120 ℃ to obtain mixed powder;
s2, activation treatment: placing the mixed powder in a vacuum oven, heating to 500 ℃ at a heating rate of 10 ℃/min, preserving heat for 4h, and naturally cooling to room temperature of 28 ℃ to obtain activated powder;
s3, modification treatment: and (3) mixing the activated powder according to the mass ratio of 1: dissolving 8 in an oxalic acid solution with the mass concentration of 20%, standing and soaking for 30min, then washing for 3 times by using deionized water, wherein the pH value of a washing solution is 7, drying for 2h at 80 ℃, then adding sodium alginate powder, crushing the sodium alginate powder, sieving by using a 60-80 mesh sieve, and shaking and mixing to obtain modified powder;
s4, coating treatment: mixing ZIF-8 crystal powder according to a mass ratio of 1:2, adding the modified powder, performing ultrasonic oscillation and mixing for 30min, then putting the mixture into a 220 ℃ oven, drying the excess water, and then preserving the heat for 3h to obtain dry ammonia adsorption material powder.
Example 8
This embodiment is substantially the same as embodiment 1, except that: the preparation method of the ZIF-8 crystal powder has different specific parameters.
The preparation method of the ZIF-8 crystal powder comprises the following steps:
s4-1: zinc nitrate hexahydrate is mixed according to the mass ratio of 1:1 is dissolved in 1.5mol/L dimethyl imidazole, mixed and kept stand for 2 hours;
s4-2: mixing a benzimidazole solution and an N, N-dimethylformamide solution according to a mass ratio of 1:3, mixing, namely adding the benzimidazole solution with the concentration of 0.8mol/L and the N, N-dimethylformamide solution with the concentration of 0.05mol/L into the mixture obtained in the step 4-1, stirring, mixing and centrifuging the mixture at the stirring speed of 50r/min, separating supernate and precipitate, washing the obtained precipitate with deionized water for 3 times, drying and crushing the washed precipitate by using a 60-mesh screen to obtain ZIF-8 crystal powder.
Example 9
This embodiment is substantially the same as embodiment 1, except that: the preparation method of the ZIF-8 crystal powder has different specific parameters.
The preparation method of the ZIF-8 crystal powder comprises the following steps:
s4-1: zinc nitrate hexahydrate is mixed according to the mass ratio of 1:1 is dissolved in 1.5mol/L dimethyl imidazole, mixed and kept stand for 2 hours;
s4-2: mixing a benzimidazole solution and an N, N-dimethylformamide solution according to a mass ratio of 1:3, mixing, namely adding the benzimidazole solution with the concentration of 0.8mol/L and the N, N-dimethylformamide solution with the concentration of 0.05mol/L into the mixture obtained in the step 4-1, stirring, mixing and centrifuging the mixture at the stirring speed of 50r/min, separating supernate and precipitate, washing the obtained precipitate with deionized water for 3 times, drying and crushing the washed precipitate by using a 80-mesh screen to obtain ZIF-8 crystal powder.
Example 10
The embodiment provides a liquid level covering ball of an ammonia adsorbing material for reducing ammonia volatilization amount on the basis of embodiment 1, as shown in fig. 1-3, the liquid level covering ball comprises a ball body 1 and a floating ring 2 sleeved outside the middle of the ball body 1, the ball body 1 and the floating ring 2 are made of polypropylene foam, the upper half part of the ball body 1 is a cavity, the lower half part of the ball body 1 is a solid structure, a main plate 3 is arranged at the center of the lower half part of the ball body 1, a plurality of slots 4 are symmetrically arranged on the lower half part of the ball body 1 at two sides of the main plate 3, spacers 5 coated with the ammonia adsorbing material are arranged between the slots 4, a plurality of through holes 6 are arranged on the lower half part of the ball body 1 in the direction perpendicular to the spacers 5, and the through holes 6 penetrate through the ball body 1, the main plate 3 and the spacers 5;
as shown in fig. 3 and 4, a slide rod 7 made of ammonia adsorbing material is arranged in the through hole 6, the slide rod 7 is connected with the main board 3 in a sliding manner, the sectional area of the two ends of the slide rod 7 is 20% larger than that of the middle part, the middle part of the slide rod 7 is connected with the pore channel arranged on the main board 3 in a sliding manner, the position of the slide rod 7 close to the two ends is provided with a limiting ring 8, the area of the limiting ring 8 is 10% smaller than that of the through hole 6, and the area of the limiting ring 8 is 30% larger than that of the pore channel;
as shown in fig. 5, the number of the spheres 1 is 4, and the spheres are connected through a polypropylene connecting rod 9, and the main plate 3 is filled with sand grains for polishing the sliding rod 7.
The working principle of ammonia adsorption through the liquid surface covering ball of the ammonia adsorption material is as follows:
float liquid level cover ball on treating adsorption solution liquid level, spheroid 1's lower half is located below the liquid level, solution flows through when the spacer 5 that is equipped with the ammonia adsorption material of coating in fluting 4 and the fluting 4, can adsorb free ammonia in the solution, and simultaneously, under the effect of hydrodynamic force, slide bar 7 makes a round trip to slide in through-hole 6 inside, simultaneously because spacing ring 8's effect can not roll off through-hole 6, and polish under the sand grain friction of filling in mainboard 3 at the middle part of slip in-process slide bar 7, in order to prolong slide bar 7's absorption life.
Example 11
This embodiment is substantially the same as embodiment 10, except that: the spheres 1 are in groups of 5.
Example 12
This embodiment is substantially the same as embodiment 10, except that: the spheres 1 are in groups of 6.
Examples of the experiments
The ammonia adsorption test was performed on the ammonia adsorbing materials prepared in examples 1 to 9, and 20g of the adsorbing materials were filled in a quartz wool adsorbing material, mixed with air as a balance gas to prepare 200ppm of ammonia mixed gas, passed through a reactor containing an adsorbent at a gas flow rate of 1L/min, and the ammonia adsorption amount of the adsorbing material was obtained by recording the outlet concentration per minute measured by an ammonia detector, and compared with the three comparative examples, and the test results are shown in table 1.
Table 1 examples 1-9 adsorption values of ammonia adsorbing materials
As can be seen from the above table, the ammonia adsorbing material prepared from the ammonia adsorbing material of example 1 according to the component mass ratio has high adsorption efficiency and saturation adsorption capacity, and the adsorption efficiency and saturation adsorption capacity of the ammonia adsorbing material prepared within the limited range of the present invention are maintained at a high level as compared with conventional materials;
the results of comparing examples 1, 4 and 5 with the adsorption material prepared from unmodified coconut shell show that the modification treatment of the coconut shell can improve the large size of the pore structure and promote the generation of activated carbon pores, thereby improving the adsorption efficiency and the saturated adsorption capacity.
As can be seen from the results of comparing examples 1, 6 and 7 with the adsorption materials prepared without adding ZIF-8 crystal powder, the adsorption stability of the ZIF-8 crystal powder can be further enhanced by coating the ZIF-8 crystal powder with modified powder, the advantage of large specific surface area can be exerted, and the adsorbed ammonia can be prevented from being desorbed again, thereby improving the adsorption efficiency and the saturation adsorption amount.
It can be seen from comparative examples 1, 8 and 9 that the process parameters for preparing ZIF-8 crystalline powder can achieve good performance in the given range of the present invention.
Claims (9)
1. An ammonia adsorbing material for reducing ammonia volatilization amount, which is characterized by comprising the following components in parts by mass: 60-70 parts of modified coconut shell activated carbon, 15-20 parts of calcium superphosphate, 75-80 parts of zinc chloride, 3-8 parts of kieselguhr, 2-4 parts of sodium alginate and 90-100 parts of ZIF-8 crystal powder, and the preparation method of the ammonia adsorption material comprises the following steps:
s1, mixing treatment: zinc chloride is added according to the mass ratio of 1:5, dissolving in water, stirring for 15min, adding modified coconut shell activated carbon, calcium superphosphate and diatomite, continuously stirring for 45min, standing for 8h, and drying at 120 ℃ for 2h to obtain mixed powder;
s2, activation treatment: placing the mixed powder in a vacuum oven, heating to 450-500 deg.C at a heating rate of 10 deg.C/min, maintaining for 4h, and naturally cooling to room temperature of 26-28 deg.C to obtain activated powder;
s3, modification treatment: and (3) mixing the activated powder according to the mass ratio of 1:8, dissolving in an oxalic acid solution with the mass concentration of 15-20%, standing and soaking for 30min, then washing for 3 times by using deionized water, wherein the pH value of a washing solution is 6.5-7, drying for 2h at the temperature of 80 ℃, adding sodium alginate powder, and shaking and mixing to obtain modified powder;
s4, coating treatment: mixing ZIF-8 crystal powder according to a mass ratio of 1:2 in proportion in deionized water, adding the modified powder, mixing for 30min by ultrasonic oscillation, then putting the mixture into a 220 ℃ oven to dry excessive water, and keeping the temperature for 3h to obtain dry ammonia adsorption material powder.
2. The ammonia adsorption material for reducing the ammonia volatilization amount according to claim 1, wherein the modified coconut shell activated carbon is prepared by the following steps: washing fresh coconut shell raw material with water content of 10-15% for 3 times, drying at 80 ℃ for 12h, crushing through a 60-80 mesh screen, and then mixing according to a mass ratio of 1:15 in proportion, dissolving in an ethanol solution with the mass concentration of 70%, carrying out ultrasonic treatment for 1h, filtering to obtain a filter cake, evaporating and recovering the residual solution, drying the filter cake for 8h at the temperature of 75 ℃ to obtain modified coconut shell powder, heating the modified coconut shell powder for 6h at the temperature of 450 ℃ to obtain modified coconut shell activated carbon, and carrying out vacuum sealing storage.
3. The ammonia adsorbing material for reducing ammonia volatilization volume according to claim 1, wherein the calcium superphosphate and the diatomite are crushed and then screened by a 60-80 mesh screen in the mixing treatment of step S1, and the stirring speed is 50-60r/min.
4. The ammonia adsorbing material for reducing ammonia volatilization volume according to claim 1, wherein the sodium alginate powder is crushed and passed through a 60-80 mesh screen in the modification treatment of step S3.
5. The ammonia adsorbing material for reducing ammonia volatilization amount according to claim 1, wherein the ZIF-8 crystal powder is prepared by the following steps in the coating process of step S4:
s4-1: zinc nitrate hexahydrate is mixed according to the mass ratio of 1:1 is dissolved in 1.5mol/L dimethyl imidazole, mixed and kept stand for 2 hours;
s4-2: mixing a benzimidazole solution and an N, N-dimethylformamide solution according to a mass ratio of 1:3, adding the mixed solution obtained in the step S4-1, stirring, mixing, centrifuging, separating supernatant and precipitate, washing the obtained precipitate for 3 times by using deionized water, drying, crushing, and screening by using a 60-80-mesh screen to obtain ZIF-8 crystal powder.
6. The ammonia adsorbing material for reducing ammonia volatilization volume according to claim 5, wherein the concentration of the benzimidazole solution in the step S4-2 is 0.8mol/L, the concentration of the N, N-dimethylformamide solution is 0.05mol/L, and the stirring speed is 50r/min.
7. The liquid level covering ball of the ammonia adsorbing material for reducing the ammonia volatilization amount according to any one of claims 1 to 6, which comprises a ball body (1) and a floating ring (2) sleeved outside the middle of the ball body (1), wherein the upper half part of the ball body (1) is a cavity, the lower half part of the ball body (1) is a solid structure, a main plate (3) is arranged in the center of the lower half part of the ball body (1), a plurality of slots (4) are symmetrically arranged on the lower half part of the ball body (1) at two sides of the main plate (3), a spacer (5) coated with the ammonia adsorbing material is arranged between the slots (4), a plurality of through holes (6) are arranged on the lower half part of the ball body (1) in the direction perpendicular to the spacer (5), the through holes (6) penetrate through the ball body (1), the main plate (3) and the spacer (5), a sliding rod (7) made of the ammonia adsorbing material is arranged inside the through holes (6), and the sliding rod (7) is connected with the main plate (3) in a sliding manner.
8. The ammonia adsorbing material liquid level covering ball for reducing ammonia volatilization according to claim 7, wherein the cross-sectional area of two ends of the sliding rod (7) is larger than that of the middle part, the middle part of the sliding rod (7) is in sliding connection with the pore channel arranged on the main plate (3), the sliding rod (7) is provided with limiting rings (8) near the two ends, and the area of the limiting rings (8) is smaller than that of the through holes (6) and larger than that of the pore channel.
9. The ammonia adsorbing material liquid level covering ball for reducing ammonia volatilization amount according to claim 7, wherein the ball bodies (1) and the floating ring (2) are made of polypropylene foam, the ball bodies (1) are in a group of 4-6 and are connected through a polypropylene connecting rod (9), and sand grains for grinding the sliding rod (7) are filled in the main plate (3).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363413A (en) * | 2014-08-22 | 2016-03-02 | 中国科学院生态环境研究中心 | Multidimensional mesoporous metal organic frameworks adsorbent and application thereof |
| CN109170741A (en) * | 2018-08-22 | 2019-01-11 | 江苏润邦食品有限公司 | A kind of stirring-type honey defecation method and adsorption cleaning sphere |
| CN111068622A (en) * | 2019-12-30 | 2020-04-28 | 葛洲坝中固科技股份有限公司 | Porous adsorption material and preparation method thereof |
| CN113402032A (en) * | 2021-07-26 | 2021-09-17 | 中水北方勘测设计研究有限责任公司 | Anti-displacement intelligent floating bed, ecological floating island, system and working method |
| CN113666449A (en) * | 2021-07-29 | 2021-11-19 | 李世杰 | Conveniently-replaced oily sewage treatment device and use method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003342530A (en) | 2002-05-30 | 2003-12-03 | Ishitake:Kk | Aqueous coating composition |
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| CN105363416B (en) * | 2015-12-07 | 2018-02-23 | 中国科学院生态环境研究中心 | Manganese dioxide nanowire@multidimensional mesoporous metal organic framework sorbents and its preparation |
| KR101991509B1 (en) | 2019-01-29 | 2019-06-19 | 최승현 | Renewable air filter for cleaning fine dust and air pollution prevention device containing the same |
| CN110655138A (en) | 2019-09-09 | 2020-01-07 | 吴承梓 | Preparation method and application of MOFs composite material |
| CN111821950A (en) | 2020-08-18 | 2020-10-27 | 湘潭大学 | Preparation method of biochar ammonia adsorbent |
| CN112915969B (en) | 2021-02-04 | 2022-07-22 | 上海交通大学 | Metal organic framework/halide composite ammonia adsorbent and preparation method thereof |
-
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-
2022
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363413A (en) * | 2014-08-22 | 2016-03-02 | 中国科学院生态环境研究中心 | Multidimensional mesoporous metal organic frameworks adsorbent and application thereof |
| CN109170741A (en) * | 2018-08-22 | 2019-01-11 | 江苏润邦食品有限公司 | A kind of stirring-type honey defecation method and adsorption cleaning sphere |
| CN111068622A (en) * | 2019-12-30 | 2020-04-28 | 葛洲坝中固科技股份有限公司 | Porous adsorption material and preparation method thereof |
| CN113402032A (en) * | 2021-07-26 | 2021-09-17 | 中水北方勘测设计研究有限责任公司 | Anti-displacement intelligent floating bed, ecological floating island, system and working method |
| CN113666449A (en) * | 2021-07-29 | 2021-11-19 | 李世杰 | Conveniently-replaced oily sewage treatment device and use method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Xiancheng Ma et al."Ammonia-treated porous carbon derived from ZIF-8 for enhanced CO2 adsorption".《Applied Surface Science》.2016,第369卷第390-397页. * |
| 王均利等."氨气吸附材料的研究进展".《过程工程学报》.2019,第19卷(第1期),第15-24页. * |
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