CN109381921B - Activated carbon for aquarium system and preparation method and application thereof - Google Patents
Activated carbon for aquarium system and preparation method and application thereof Download PDFInfo
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- CN109381921B CN109381921B CN201811212302.XA CN201811212302A CN109381921B CN 109381921 B CN109381921 B CN 109381921B CN 201811212302 A CN201811212302 A CN 201811212302A CN 109381921 B CN109381921 B CN 109381921B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
- B01D39/06—Inorganic material, e.g. asbestos fibres, glass beads or fibres
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
Abstract
The invention discloses an active carbon for an aquarium system and a preparation method and application thereof, wherein the preparation method comprises the following steps: dipping the activated carbon in a metal salt solution, and then drying, wherein the metal salt is a mixture consisting of two or more than two of water-soluble metal salts of iron, aluminum, zinc, copper and manganese; and calcining the activated carbon absorbing the metal salt solution under the condition of isolating the air to obtain the metal salt solution. The filtering material of aquatic system made of the active carbon can effectively decompose the pollutants in water, inhibit the propagation of harmful bacteria, maintain excellent water quality condition, and can stably play a role for a long time along with the peeling and updating of the surface of the active carbon.
Description
Technical Field
The invention relates to an active carbon for an aquarium system and a preparation method and application thereof.
Background
The filtering system is an essential component of the aquarium system, namely impurities, residual baits, organic wastes and the like in water are filtered by utilizing the characteristics of the filtering material, so that various indexes of the water are regulated, the water quality of the aquarium system is kept to be suitable for living organisms, and the water quality in the aquarium system is kept to be stable. Activated carbon is a porous carbonaceous material with a highly developed pore structure, is an excellent adsorbent, and is one of the common filtering materials in aquarium systems, and many filters are filled with activated carbon inside their housings for adsorbing and filtering harmful substances such as organic wastes, free substances, microorganisms and the like in water and reducing the turbidity of water. The activated carbon can form a layer of balanced surface concentration on the particle surface, and then organic substance impurities are adsorbed into the activated carbon particles, although the adsorption effect in the initial stage of use is very high, the adsorption capacity of the activated carbon is weakened to different degrees along with the increase of the use time, the adsorption effect is also reduced, if the water quality in the aquarium is turbid, the content of organic matters in the water is high, the activated carbon can quickly lose the filtering function, and therefore, the activated carbon is required to be cleaned or replaced regularly. In addition, the activated carbon on the market can only adsorb harmful substances in water, cannot degrade the harmful substances, and does not have a sterilization function, so that the effect of maintaining water quality can be achieved by assistance of chemical filtration, biological filtration and the like.
At present, some modified activated carbons can achieve better wastewater treatment effect by utilizing the electrode characteristics. The invention discloses a metal modified activated carbon fiber electrode and a method for removing nitrate by using the same (patent number: 200410098590.2), and discloses a modified activated carbon fiber which can reduce nitrate in water under the condition of electrifying. The invention provides modified activated carbon and application thereof (patent number: 201010501795.6), which can effectively exert the high-efficiency catalytic degradation capability of transition metal on ozone and can be used for removing various pollutants in water. The invention provides an activated carbon fiber three-dimensional particle electrode catalyst and a preparation method thereof (patent number: 201810016187.2), which can remove organic pollutants in wastewater under the condition of electrification. However, the electrodes are made of noble metals, the cost is high, the reaction can be carried out only by applying an external current, in addition, the pH value of the water body is continuously increased by the hydroxyl free radicals released in the treatment process, and once the pH value exceeds the range of the pH value which can be tolerated by organisms, the organisms are killed, so that the electrodes are not suitable for the aquatic animal system with living organisms.
Disclosure of Invention
The invention aims to provide activated carbon for an aquarium system and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
an activated carbon for an aquarium system is prepared by the following steps:
1) dipping the activated carbon in a metal salt solution, and then drying, wherein the metal salt is a mixture consisting of two or more than two of water-soluble metal salts of iron, aluminum, zinc, copper and manganese;
2) and calcining the activated carbon absorbing the metal salt solution under the condition of isolating the air to obtain the metal salt solution.
Further, the metal salt is one of the following mixtures:
a mixture of water-soluble metal salts of iron and aluminum;
water-soluble metal salt mixtures of iron, aluminum, copper;
water-soluble metal salt mixtures of iron, aluminum, zinc, manganese;
water soluble metal salt mixture of iron, aluminum, copper, zinc, manganese.
Further, the metal salt is one of the following mixtures:
the mass ratio of the water-soluble metal salt of iron to the water-soluble metal salt of aluminum (30-40): (5-15) mixing the above components;
the mass ratio of the water-soluble metal salts of iron, aluminum and copper is (30-35): (5-15): (1-8) mixing;
a mixture of water-soluble metal salts of iron, aluminum, zinc and manganese in a mass ratio of (20-30) to (5-15) to (3-7);
the water-soluble metal salts of iron, aluminum, copper, zinc and manganese are mixed in a mass ratio of (20-30) to (5-15) to (1-8) to (3-7).
Further, the metal salt is one of the following mixtures:
the mass ratio of the water-soluble metal salt of iron to the water-soluble metal salt of aluminum is 35: 10 of a mixed mixture;
the mass ratio of the water-soluble metal salts of iron, aluminum and copper is (30-35): (5-15): (3-5) mixing;
the mixture is formed by mixing water-soluble metal salts of iron, aluminum, zinc and manganese in a mass ratio of 25 (5-10) to 5: 5.
Further, the calcination temperature is 400-1100 ℃.
Further, the calcination temperature is 400-700 ℃.
Further, the calcination time is 1-5 hours.
Furthermore, the calcination time is 1.5-4 hours.
Further, the activated carbon is commercially available activated carbon, the shape and size of which are not limited, and preferably the activated carbon has a small particle diameter, preferably 0.1 to 20 mm.
A filter material contains the active carbon for the aquatic animal system, and also contains one or more of an acidifier and a catalyst, wherein the catalyst is an electrolyte, a conductor or a substance capable of generating hydroxyl radicals or oxygen through a hydrolysis reaction.
Further, the catalyst comprises one or more of calcium peroxide, calcium oxide, calcium carbonate, calcium hydroxide and silicon dioxide.
Further, the acidulant comprises one or more of hydrochloric acid, phosphoric acid, malic acid, citric acid, fumaric acid, lactic acid, formic acid, acetic acid, propionic acid, butyric acid, sorbic acid.
Further, the preparation method of the aquarium system filter material comprises the following steps: respectively soaking the activated carbon for the aquarium system in an aqueous solution of a catalyst or an acidifier, and drying to obtain the activated carbon;
the mass ratio of the metal salt, the catalyst and the acidifying agent loaded on the activated carbon is (0.2-0.7): (0.03-0.3): (0.03-0.3).
Further, the mass ratio of the metal salt, the catalyst and the acidifying agent loaded on the activated carbon is (0.2-0.7): (0.05-0.2): (0.05-0.2).
Further, the preparation method of the aquarium system filter material comprises the following steps:
preparing an acidifier with a slow-release function: the acidifier and the excipient are uniformly mixed in proportion and then uniformly embedded by the sustained-release material in proportion to prepare the acidifier with the sustained-release function, wherein the acidifier: excipient: the mass ratio of the slow-release material is 1: (0.1-0.5): (0.3-1), wherein the excipient is silicon dioxide;
grinding and uniformly mixing the activated carbon, the catalyst and the acidifier with the slow-release function for the aquarium system, and bonding the components by using an adhesive to prepare particles;
the mass ratio of the active carbon, the metal salt, the catalyst, the acidifying agent with the slow release function and the adhesive used for the aquatic system in the filter material is (0.2-0.5): (0.2-0.6): (0.03-0.1): (0.02-0.1): (0.02-0.1).
Further, the slow release material is one or more of ethyl cellulose, hydroxypropyl methyl cellulose, acrylic resin, shellac, sodium alginate, maltodextrin, modified starch, stearic acid, magnesium stearate, sodium carboxymethylcellulose and xanthan gum.
Further, the adhesive is one or more of clay, sodium silicate, polyvinyl alcohol and sodium carboxymethyl cellulose.
The filter material is applied to the in-situ water body treatment of the aquatic animal culture system.
The invention has the beneficial effects that:
1. the filter material can generate hydroxyl free radicals with strong oxidizing power in water, can degrade organic wastes and can sterilize. In addition, due to the consumption of the filtering material, the activated carbon can drift out along with water in a powder form, and the surface is peeled off and renewed, so that the water purifying effect can be kept for a long time.
2. The added metal is a compound of various metals, and iron ions, aluminum ions and zinc ions generated in the using process are combined with hydroxyl radicals to generate iron hydroxide, aluminum hydroxide and zinc hydroxide which can be used as a flocculating agent for sustained release to deposit organic matters and impurities in water so as to achieve the effect of clarifying water quality.
3. The invention can selectively add different catalysts according to different culture conditions and water quality conditions to increase the dissolved oxygen in water and the oxidation reaction of organic wastes.
4. The acidifying agent added in the invention is intermediate acid in physiological reaction, has no harmful effect on organisms, can achieve the bacteriostatic effect, simultaneously can maintain the microenvironment of electrolytic reaction at acidity, is beneficial to reducing the phenomena of agglomeration, short flow, channeling and the like in activated carbon, solves the problem that water gradually becomes alkali and is not beneficial to the survival of organisms, and can maintain the pH value close to neutral under the action of the acidifying agent, so that the water treated by the filtering material can be directly recycled in an aquatic system.
Drawings
FIG. 1 is a graph of COD concentration of a water body over time during aquarium treatment with different filter materials;
FIG. 2 is a graph showing the change of the ammonia nitrogen concentration of the water body with time in the process of treating the aquarium by different filter materials;
FIG. 3 is a graph of nitrate concentration in a water body over time during treatment of an aquarium with different filter materials;
FIG. 4 is a graph of nitrite concentration in a water body over time during aquarium treatment with different filter materials;
FIG. 5 is a graph of dissolved oxygen concentration of a body of water over time during treatment of an aquarium with different filter materials;
FIG. 6 is a graph of bacterial content of a body of water as a function of time during treatment of an aquarium with different filter materials;
FIG. 7 is a graph showing the change of pH value of water body with time during the treatment of aquarium with different filtering materials.
Detailed Description
The present invention will be described in further detail with reference to examples. It will also be understood that the following examples are included merely for purposes of further illustrating the invention and are not to be construed as limiting the scope of the invention, as the invention extends to insubstantial modifications and adaptations of the invention following in the light of the principles set forth herein. The specific process parameters and the like of the following examples are also only one example of suitable ranges, and the skilled person can make a selection within the suitable ranges through the description herein, and are not limited to the specific data of the following examples.
Example 1
A filter material for an aquarium system, which is prepared by the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 30 ℃, wherein the dipping time of each metal salt solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 500 ℃ for 4 hours under the condition of isolating the air, and naturally cooling to room temperature.
3) Sequentially dipping the calcined activated carbon in aqueous solutions of a catalyst and an acidifying agent at the temperature of 30 ℃, wherein the dipping time of each aqueous solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solutions are completely absorbed, thus obtaining the activated carbon.
The proportion of the metal salt, the catalyst and the acidifying agent loaded on the activated carbon is as follows: 50:15:10.
Wherein the content of the first and second substances,
the metal salt is ferric salt, aluminum salt, zinc salt and manganese salt, and the mass ratio of the ferric salt to the aluminum salt to the zinc salt to the manganese salt is 30:10:5: 5.
The catalyst is as follows: calcium carbonate and calcium hydroxide, the mass ratio of calcium carbonate to calcium hydroxide is: 0.5:1.
The acidifier is: phosphoric acid, hydrochloric acid and citric acid, wherein the mass ratio of the phosphoric acid to the hydrochloric acid to the citric acid is 1:0.5: 0.5.
Example 2
A filter material for an aquarium system, which is prepared by the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 30 ℃, wherein the dipping time of each metal salt solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 500 ℃ for 4 hours under the condition of isolating the air, and naturally cooling to room temperature.
3) Sequentially dipping the calcined activated carbon in aqueous solutions of a catalyst and an acidifying agent at the temperature of 30 ℃, wherein the dipping time of each aqueous solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solutions are completely absorbed, thus obtaining the activated carbon.
The proportion of the metal salt, the catalyst and the acidifying agent loaded on the activated carbon is as follows: 50:10:15.
Wherein the content of the first and second substances,
the metal salt is ferric salt, aluminum salt, zinc salt and manganese salt, and the mass ratio of the ferric salt to the aluminum salt to the zinc salt to the manganese salt is 30:10:5: 5.
The catalyst is as follows: the calcium peroxide, the calcium oxide and the calcium carbonate are in the mass ratio: 1:1:1.
The acidifier is: phosphoric acid and lactic acid, wherein the mass ratio of the phosphoric acid to the lactic acid is 0.5: 1.
Example 3
A filter material for an aquarium system, the filter material comprising the following components:
40% of activated carbon, 30% of iron salt, 10% of aluminum salt, 3% of copper salt, 5% of adhesive, 5% of catalyst and 7% of acidifying agent with slow release function.
Wherein the content of the first and second substances,
adhesive: the mass ratio of polyvinyl alcohol to sodium carboxymethylcellulose is 1:1, mixing the mixture;
catalyst: calcium peroxide, calcium oxide and silicon dioxide are mixed according to the mass ratio of 1:0.5: 0.2 blend of
Acidifying agent with slow release function: phosphoric acid, citric acid and lactic acid in a mass ratio of 1:1:1, then uniformly mixing with silicon dioxide, and embedding the mixture through a slow-release material, wherein the mass ratio of the acidifier to the silicon dioxide to the slow-release material is 1:0.5: 0.8, the slow release material is shellac and magnesium stearate in a mass ratio of 1:1, mixing the mixture.
The preparation method of the filter material comprises the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 40 ℃, wherein the dipping time of each metal salt solution is 3 hours, drying at the temperature of 100 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) The activated carbon completely absorbing the metal salt solution is calcined for 1.5 hours at 700 ℃ under the condition of air isolation, and is naturally cooled to the room temperature.
3) Grinding and uniformly mixing the calcined activated carbon, the catalyst and the acidifier with the slow release function according to the mass ratio, and then bonding the components by using an adhesive to prepare particles with the diameter of 0.5mm, thus obtaining the catalyst.
Example 4
A filter material for an aquarium system, the filter material comprising the following components:
40% of activated carbon, 30% of iron salt, 5% of aluminum salt, 5% of copper salt, 5% of adhesive, 8% of catalyst and 7% of acidifying agent with slow release function.
Wherein the content of the first and second substances,
adhesive: sodium silicate;
catalyst: calcium peroxide and calcium carbonate are mixed according to the mass ratio of 1:0.5 blend mixture
Acidifying agent with slow release function: the phosphoric acid and the silicon dioxide are uniformly mixed and are embedded through the slow-release material, wherein the mass ratio of the acidifying agent to the silicon dioxide to the slow-release material is 1:0.5: 0.8, the slow release material is stearic acid and magnesium stearate in a mass ratio of 1:1, mixing the mixture.
The preparation method of the filter material comprises the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 40 ℃, wherein the dipping time of each metal salt solution is 3 hours, drying at the temperature of 100 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) The activated carbon completely absorbing the metal salt solution is calcined for 1.5 hours at 700 ℃ under the condition of air isolation, and is naturally cooled to the room temperature.
3) Grinding and uniformly mixing the calcined activated carbon, the catalyst and the acidifier with the slow release function according to the mass ratio, and then bonding the components by using an adhesive to prepare particles with the diameter of 0.5mm, thus obtaining the catalyst.
Example 5
A filter material for an aquarium system, which is prepared by the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 35 ℃, wherein the dipping time of each metal salt solution is 1.5 hours, drying at the temperature of 80 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 600 ℃ for 3 hours under the condition of isolating the air, and naturally cooling to room temperature.
3) Sequentially dipping the calcined activated carbon in aqueous solutions of a catalyst and an acidifier at the temperature of 35 ℃, drying the aqueous solutions at the temperature of 80 ℃ until the solutions are completely absorbed, and thus obtaining the catalyst.
The proportion of the metal salt, the catalyst and the acidifying agent loaded on the activated carbon is as follows: 55:17:8.
Wherein the content of the first and second substances,
the metal salt is ferric salt, aluminum salt and copper salt, and the mass ratio of the ferric salt to the aluminum salt to the copper salt is 35:15: 5.
The catalyst is as follows: the calcium peroxide, the calcium oxide and the silicon dioxide are in the mass ratio: 1:0.5:0.5.
The acidifier is: phosphoric acid and fumaric acid, wherein the mass ratio of the phosphoric acid to the fumaric acid is 1: 1.
Example 6
A filter material for an aquarium system, which is prepared by the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 35 ℃, wherein the dipping time of each metal salt solution is 1.5 hours, drying at the temperature of 80 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 600 ℃ for 3 hours under the condition of isolating the air, and naturally cooling to room temperature.
3) Sequentially dipping the calcined activated carbon in aqueous solutions of a catalyst and an acidifier at the temperature of 35 ℃, drying the aqueous solutions at the temperature of 80 ℃ until the solutions are completely absorbed, and thus obtaining the catalyst.
The proportion of the metal salt, the catalyst and the acidifying agent loaded on the activated carbon is as follows: 55:15:10.
Wherein the content of the first and second substances,
the metal salt is ferric salt, aluminum salt and copper salt, and the mass ratio of the ferric salt to the aluminum salt to the copper salt is 35:15: 5.
The catalyst is as follows: the calcium peroxide and the calcium hydroxide are in the mass ratio: 0.5:1.
The acidifier is: hydrochloric acid, malic acid and citric acid, wherein the mass ratio of the hydrochloric acid to the malic acid to the citric acid is 1:1: 1.
Example 7
A filter material for an aquarium system, the filter material comprising the following components:
35% of activated carbon, 35% of iron salt, 10% of aluminum salt, 8% of adhesive, 7% of catalyst and 5% of acidifying agent with slow release function.
Wherein the content of the first and second substances,
adhesive: sodium silicate;
catalyst: calcium peroxide and calcium carbonate are mixed according to the mass ratio of 1:1, mixing the mixture;
acidifying agent with slow release function: the phosphoric acid and the silicon dioxide are uniformly mixed and are embedded through the slow-release material, wherein the mass ratio of the acidifying agent to the silicon dioxide to the slow-release material is 1: 0.6: 0.4, the slow release material is acrylic resin.
The preparation method of the filter material comprises the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 50 ℃, wherein the dipping time of each metal salt solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 400 ℃ for 2 hours under the condition of isolating the air, and naturally cooling to room temperature.
3) Grinding and uniformly mixing the calcined activated carbon, the catalyst and the acidifier with the slow release function according to the mass ratio, and then bonding the components by using an adhesive to prepare particles with the diameter of 0.5mm, thus obtaining the catalyst.
Example 8
A filter material for an aquarium system, the filter material comprising the following components:
35% of activated carbon, 35% of iron salt, 10% of aluminum salt, 8% of adhesive, 5% of catalyst and 7% of acidifying agent with slow release function.
Wherein the content of the first and second substances,
adhesive: polyvinyl alcohol;
catalyst: calcium oxide;
acidifying agent with slow release function: the hydrochloric acid, the citric acid and the fumaric acid are mixed according to the mass ratio of 1:1:1, are uniformly mixed with the silicon dioxide, and are embedded through the slow-release material, wherein the mass ratio of the acidifying agent to the silicon dioxide to the slow-release material is 1: 0.6: 0.4, the slow release material is a mixture of stearic acid and magnesium stearate mixed according to the mass ratio of 1: 1.
The preparation method of the filter material comprises the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 50 ℃, wherein the dipping time of each metal salt solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 400 ℃ for 2 hours under the condition of isolating the air, and naturally cooling to room temperature.
Grinding and uniformly mixing the calcined activated carbon, the catalyst and the acidifier with the slow release function according to the mass ratio, and then bonding the components by using an adhesive to prepare particles with the diameter of 0.5mm, thus obtaining the catalyst.
Comparative example 1
A filter material for an aquarium system, which is prepared by the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 30 ℃, wherein the dipping time of each metal salt solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 500 ℃ for 4 hours under the condition of isolating the air, and naturally cooling to room temperature.
3) Sequentially soaking the calcined activated carbon in aqueous solutions of acidifying agents at the temperature of 30 ℃ for 2 hours, drying at the temperature of 120 ℃, and repeatedly soaking until the solutions are completely absorbed to obtain the activated carbon.
The ratio of the metal salt and the acidifier loaded on the activated carbon is as follows: 50:15.
Wherein the content of the first and second substances,
the metal salt is ferric salt, aluminum salt, zinc salt and manganese salt, and the mass ratio of the ferric salt to the aluminum salt to the zinc salt to the manganese salt is 30:10:5: 5.
The acidifier is: phosphoric acid, hydrochloric acid, citric acid, phosphoric acid and hydrochloric acid, wherein the mass ratio of the citric acid to the phosphoric acid is 1:1: 1.
Comparative example 2
A filter material for an aquarium system, which is prepared by the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 30 ℃, wherein the dipping time of each metal salt solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 500 ℃ for 4 hours under the condition of isolating the air, and naturally cooling to room temperature.
3) Sequentially dipping the calcined activated carbon in aqueous solutions of the catalyst at the temperature of 30 ℃, wherein the dipping time of each aqueous solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solution is completely absorbed, thus obtaining the catalyst.
The ratio of the metal salt and the catalyst loaded on the activated carbon is as follows: 50:15.
Wherein the content of the first and second substances,
the metal salt is ferric salt, aluminum salt, zinc salt and manganese salt, and the mass ratio of the ferric salt to the aluminum salt to the zinc salt to the manganese salt is 30:10:5: 5.
The catalyst is as follows: calcium peroxide, calcium oxide and silicon dioxide, wherein the mass ratio of the calcium peroxide to the calcium oxide to the silicon dioxide is 1:0.5: 0.5.
Comparative example 3
A filter material for an aquarium system, which is prepared by the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 30 ℃, wherein the dipping time of each metal salt solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 500 ℃ for 4 hours under the condition of isolating the air, and naturally cooling to room temperature.
3) Sequentially dipping the calcined activated carbon in aqueous solutions of a catalyst and an acidifying agent at the temperature of 30 ℃, wherein the dipping time of each aqueous solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solutions are completely absorbed, thus obtaining the activated carbon.
The proportion of the metal salt, the catalyst and the acidifying agent loaded on the activated carbon is as follows: 50:15:10.
Wherein the content of the first and second substances,
the metal salt is iron salt.
The catalyst is as follows: calcium carbonate and calcium hydroxide, the mass ratio of calcium carbonate to calcium hydroxide is: 0.5:1.
The acidifier is: phosphoric acid, hydrochloric acid and citric acid, wherein the mass ratio of the phosphoric acid to the hydrochloric acid to the citric acid is 1:0.5: 0.5.
Comparative example 4
A filter material for an aquarium system, the filter material comprising the following components:
40% of activated carbon, 25% of iron salt, 10% of aluminum salt, 5% of zinc salt, 5% of manganese salt, 5% of adhesive and 10% of acidifying agent with a slow-release function.
Wherein the content of the first and second substances,
adhesive: the clay and the sodium carboxymethyl cellulose are mixed according to the mass ratio of 1:1, mixing the mixture;
acidifying agent with slow release function: the fumaric acid and the silicon dioxide are uniformly mixed and embedded through the slow-release material, wherein the mass ratio of the acidifying agent to the silicon dioxide to the slow-release material is 1:0.5: 0.8, the slow release material is shellac and sodium hydroxymethyl cellulose in a mass ratio of 1:1, mixing the mixture.
The preparation method of the filter material comprises the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 40 ℃, wherein the dipping time of each metal salt solution is 3 hours, drying at the temperature of 100 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) The activated carbon completely absorbing the metal salt solution is calcined for 1.5 hours at 700 ℃ under the condition of air isolation, and is naturally cooled to the room temperature.
Grinding and uniformly mixing the calcined activated carbon and the acidifier with the slow release function according to the mass ratio, and bonding the components by using an adhesive to prepare particles with the diameter of 0.5 mm.
Comparative example 5
A filter material for an aquarium system, the filter material comprising the following components:
40% of activated carbon, 30% of iron salt, 5% of aluminum salt, 3% of copper salt, 5% of adhesive and 15% of catalyst.
Wherein the content of the first and second substances,
adhesive: sodium silicate and polyvinyl alcohol in a mass ratio of 1:1, mixing the mixture;
catalyst: a mixture of calcium peroxide, calcium carbonate and calcium hydroxide in a mass ratio of 1:1:0.5
The preparation method of the filter material comprises the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 40 ℃, wherein the dipping time of each metal salt solution is 3 hours, drying at the temperature of 100 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) The activated carbon completely absorbing the metal salt solution is calcined for 1.5 hours at 700 ℃ under the condition of air isolation, and is naturally cooled to the room temperature.
Grinding and uniformly mixing the calcined activated carbon and the catalyst according to the mass ratio, and then bonding the components by using an adhesive to prepare particles with the diameter of 0.5mm, thus obtaining the catalyst.
Comparative example 6
A filter material for an aquarium system, the filter material comprising the following components:
40% of activated carbon, 40% of iron salt, 5% of adhesive, 5% of catalyst and 7% of acidifier with slow release function.
Wherein the content of the first and second substances,
adhesive: the mass ratio of polyvinyl alcohol to sodium carboxymethylcellulose is 1:1, mixing the mixture;
catalyst: calcium peroxide, calcium oxide and silicon dioxide are mixed according to the mass ratio of 1:0.5: 0.2 blend of
Acidifying agent with slow release function: phosphoric acid, citric acid and lactic acid in a mass ratio of 1:1:1, then uniformly mixing with silicon dioxide, and embedding the mixture through a slow-release material, wherein the mass ratio of the acidifier to the silicon dioxide to the slow-release material is 1:0.5: 0.8, the slow release material is shellac and magnesium stearate in a mass ratio of 1:1, mixing the mixture.
The preparation method of the filter material comprises the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 40 ℃, wherein the dipping time of each metal salt solution is 3 hours, drying at the temperature of 100 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) The activated carbon completely absorbing the metal salt solution is calcined for 1.5 hours at 700 ℃ under the condition of air isolation, and is naturally cooled to the room temperature.
Grinding and uniformly mixing the calcined activated carbon, the catalyst and the acidifier with the slow release function according to the mass ratio, and then bonding the components by using an adhesive to prepare particles with the diameter of 0.5mm, thus obtaining the catalyst.
Comparative example 7
A filter material for an aquarium system, which is prepared by the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 35 ℃, wherein the dipping time of each metal salt solution is 1.5 hours, drying at the temperature of 80 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 600 ℃ for 3 hours under the condition of isolating the air, and naturally cooling to room temperature.
3) Sequentially soaking the calcined activated carbon in an aqueous solution of an acidifying agent at the temperature of 35 ℃ for 1.5 hours, drying at the temperature of 80 ℃, and repeatedly soaking until the solution is completely absorbed to obtain the activated carbon.
The ratio of the metal salt and the acidifier loaded on the activated carbon is as follows: 55:15.
Wherein the content of the first and second substances,
the metal salt is ferric salt, aluminum salt and copper salt, and the mass ratio of the ferric salt to the aluminum salt to the copper salt is 35:15: 5.
The acidifier is: phosphoric acid, hydrochloric acid and formic acid, wherein the mass ratio of the phosphoric acid to the hydrochloric acid to the formic acid is 0.5:0.5: 1.
Comparative example 8
A filter material for an aquarium system, which is prepared by the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 35 ℃, wherein the dipping time of each metal salt solution is 1.5 hours, drying at the temperature of 80 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 600 ℃ for 3 hours under the condition of isolating the air, and naturally cooling to room temperature.
3) And (3) sequentially dipping the calcined activated carbon in aqueous solutions of the catalyst at the temperature of 35 ℃, wherein the dipping time of each aqueous solution is 1.5 hours, drying at the temperature of 80 ℃, and repeatedly dipping until the solutions are completely absorbed, thus obtaining the catalyst.
The ratio of the metal salt and the catalyst loaded on the activated carbon is as follows: 55:20.
Wherein the content of the first and second substances,
the metal salt is ferric salt, aluminum salt and copper salt, and the mass ratio of the ferric salt to the aluminum salt to the copper salt is 35:15: 5.
The catalyst is as follows: the calcium peroxide, the calcium carbonate and the silicon dioxide are mixed according to a mass ratio of 1:0.5: 0.3.
Comparative example 9
A filter material for an aquarium system, which is prepared by the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 35 ℃, wherein the dipping time of each metal salt solution is 1.5 hours, drying at the temperature of 80 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 600 ℃ for 3 hours under the condition of isolating the air, and naturally cooling to room temperature.
3) Sequentially dipping the calcined activated carbon in aqueous solutions of a catalyst and an acidifier at the temperature of 35 ℃, drying the aqueous solutions at the temperature of 80 ℃ until the solutions are completely absorbed, and thus obtaining the catalyst.
The proportion of the metal salt, the catalyst and the acidifying agent loaded on the activated carbon is as follows: 50:17:8.
Wherein the content of the first and second substances,
the metal salt is iron salt.
The catalyst is as follows: the calcium peroxide, the calcium oxide and the silicon dioxide are in the mass ratio: 1:0.5:0.5.
The acidifier is: phosphoric acid and fumaric acid, wherein the mass ratio of the phosphoric acid to the fumaric acid is 1: 1.
Comparative example 10
A filter material for an aquarium system, the filter material comprising the following components:
35% of activated carbon, 35% of iron salt, 10% of aluminum salt, 5% of copper salt, 10% of adhesive and 10% of acidifying agent with slow release function.
Wherein the content of the first and second substances,
adhesive: sodium carboxymethylcellulose;
acidifying agent with slow release function: phosphoric acid and lactic acid are mixed according to the mass ratio of 0.5:1, then are uniformly mixed with silicon dioxide, and are embedded through a slow-release material, wherein the mass ratio of the acidifying agent to the silicon dioxide to the slow-release material is 1: 0.6: 0.4, the slow release material is a mixture of sodium carboxymethyl cellulose and acrylic resin mixed in a ratio of 1: 1.
The preparation method of the filter material comprises the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 50 ℃, wherein the dipping time of each metal salt solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 400 ℃ for 2 hours under the condition of isolating the air, and naturally cooling to room temperature.
Grinding and uniformly mixing the calcined activated carbon and the acidifier with the slow release function according to the mass ratio, and bonding the components by using an adhesive to prepare particles with the diameter of 0.5 mm.
Comparative example 11
A filter material for an aquarium system, the filter material comprising the following components:
35% of activated carbon, 35% of iron salt, 10% of aluminum salt, 5% of copper salt, 10% of adhesive and 10% of catalyst.
Wherein the content of the first and second substances,
adhesive: clay;
catalyst: calcium peroxide, calcium carbonate and silicon dioxide are mixed according to the mass ratio of 1:1:0.5 of the mixed mixture;
the preparation method of the filter material comprises the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 50 ℃, wherein the dipping time of each metal salt solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 400 ℃ for 2 hours under the condition of isolating the air, and naturally cooling to room temperature.
Grinding and uniformly mixing the calcined activated carbon and the catalyst according to the mass ratio, and then bonding the components by using an adhesive to prepare particles with the diameter of 0.5mm, thus obtaining the catalyst.
Comparative example 12
A filter material for an aquarium system, the filter material comprising the following components:
35% of activated carbon, 40% of iron salt, 8% of adhesive, 7% of catalyst and 5% of acidifier with slow release function.
Wherein the content of the first and second substances,
adhesive: sodium silicate;
catalyst: calcium peroxide and calcium carbonate are mixed according to the mass ratio of 1:1, mixing the mixture;
acidifying agent with slow release function: the phosphoric acid and the silicon dioxide are uniformly mixed and are embedded through the slow-release material, wherein the mass ratio of the acidifying agent to the silicon dioxide to the slow-release material is 1: 0.6: 0.4, the slow release material is acrylic resin.
The preparation method of the filter material comprises the following steps:
1) sequentially dipping the activated carbon into metal salt solutions at the temperature of 50 ℃, wherein the dipping time of each metal salt solution is 2 hours, drying at the temperature of 120 ℃, and repeatedly dipping until the solutions are completely absorbed.
2) And calcining the activated carbon completely absorbing the metal salt solution at 400 ℃ for 2 hours under the condition of isolating the air, and naturally cooling to room temperature.
Grinding and uniformly mixing the calcined activated carbon, the catalyst and the acidifier with the slow release function according to the mass ratio, and then bonding the components by using an adhesive to prepare particles with the diameter of 0.5mm, thus obtaining the catalyst.
The filtering materials in the embodiments 1-4 and the comparative examples 1-6 are respectively applied to a closed fresh water aquatic animal system with serious pollution degree and higher culture density, and the volume ratio of the mass of the filtering material to the water body is 1: 20g/mL, the water quality improvement is as follows:
the filtering materials in the embodiments 5-8 and the comparative examples 7-12 are respectively applied to the closed seawater aquarium system with serious pollution degree and higher culture density, and the volume ratio of the mass of the filtering material to the water body is 1: 20g/mL, the water quality improvement is as follows:
filter effect detection
Choose 6 groups of aquarium that do not take the filter for use, contain the fresh water of 15 liters volumes in every group of aquarium, 5 strips length of raising of every group are 20 ~ 25cm, healthy carp, and the equivalent feed is normally thrown to feed every day to carry out following processing to 6 groups of aquarium at the experiment initiation:
experimental group 1: no treatment is carried out;
experimental group 2: putting commercially available traditional aquarium culture activated carbon (the diameter of the granular activated carbon is 1mm) into an aquarium;
experimental group 3: putting a commercial aquarium culture filter material-biological ball (containing nitrifying bacteria) into an aquarium;
experimental group 4: activated carbon (particle diameter of 1mm) containing iron (50% activated carbon loading) was placed in an aquarium without adding an acidifying agent and a catalyst, and the other preparation methods were the same as those of the activated carbon preparation method of example 1;
test group 5: activated carbon having the same composition as in example 1 of the present invention was placed in an aquarium, however, it was not subjected to high-temperature calcination (granular activated carbon having a diameter of 1mm) during the preparation process;
experimental group 6: the activated carbon of example 1 of the present invention (granular activated carbon having a diameter of 1mm) was put in an aquarium;
the filter materials of the above experiments were placed in filter boxes of the same type, and the mass to total water volume ratio of the filter materials used was 750 g: and 15L, placing the filter boxes containing the filter materials in the water body of the aquarium, connecting the filter boxes with an air pump, filtering the water through the filter boxes of each group, returning the filtered water into the aquarium again, and circulating the steps.
The COD, ammonia nitrogen, nitrate and nitrite concentration, dissolved oxygen, bacteria content and pH value in the water body are tested every 10 days, and the results are shown in the figure 1-7:
as can be seen from FIGS. 1 to 7: the water quality condition of the test group 1 without any treatment rapidly deteriorated after the test day 10; the experimental group 2 using the commercially available conventional aquarium culture activated carbon has a good adsorption and treatment effect at the initial stage, but the treatment effect after 30 days becomes worse gradually with the loss of the filter material; the experimental group 3 of the biological ball which is a filter material for culturing the commercial aquarium needs time to fix the effective bacteria and exert the functions, so the early treatment effect is not obvious, and the later effect is changed according to the fixing state and the water quality condition; experimental group 4 using activated carbon containing iron (50% activated carbon loading), but the ph was neutral, the filtration effect was limited, and the water in the aquarium became alkaline with long term use, which was detrimental to the survival of the organisms; the filter material in test set 5 worked better than the other sets, but there was a gap in the performance compared to the filter material in example 1. The experimental group 6 using the filter material of example 1 of the present invention can immediately take effect when the filter material is put into water, decompose pollutants in water, inhibit the propagation of harmful bacteria, maintain excellent water quality conditions, and simultaneously, can stably exert effects for a long time along with the exfoliation and renewal of the surface of the activated carbon.
Claims (8)
1. A filter material, characterized by: contains activated carbon used for aquarium systems, and the filter material also contains an acidifier and a catalyst, wherein the catalyst is an electrolyte, a conductor or a substance which can generate hydroxyl radicals or oxygen through hydrolysis reaction;
the preparation method of the activated carbon for the aquarium system comprises the following steps:
1) dipping activated carbon in a metal salt solution, and then drying;
2) calcining the activated carbon absorbing the metal salt solution under the condition of isolating air to obtain the metal salt solution;
wherein the metal salt is one of the following mixtures:
a mixture of water-soluble metal salts of iron and aluminum;
water-soluble metal salt mixtures of iron, aluminum, copper;
water-soluble metal salt mixtures of iron, aluminum, zinc, manganese;
water soluble metal salt mixture of iron, aluminum, copper, zinc, manganese.
2. The filter material of claim 1, wherein: the metal salt is one of the following mixtures:
the mass ratio of the water-soluble metal salt of iron to the water-soluble metal salt of aluminum (30-40): (5-15) mixing the above components;
the mass ratio of the water-soluble metal salts of iron, aluminum and copper is (30-35): (5-15): (1-8) mixing;
a mixture of water-soluble metal salts of iron, aluminum, zinc and manganese in a mass ratio of (20-30) to (5-15) to (3-7);
the water-soluble metal salts of iron, aluminum, copper, zinc and manganese are mixed in a mass ratio of (20-30) to (5-15) to (1-8) to (3-7).
3. The filter material of claim 1, wherein: the calcination temperature is 400-1100 ℃.
4. The filter material of claim 1, wherein: the catalyst comprises one or more of calcium peroxide, calcium oxide, calcium carbonate, calcium hydroxide and silicon dioxide.
5. The filter material of claim 1, wherein: the acidulant comprises one or more of hydrochloric acid, phosphoric acid, malic acid, citric acid, fumaric acid, lactic acid, formic acid, acetic acid, propionic acid, butyric acid, and sorbic acid.
6. The filter material of claim 1, wherein: the preparation method of the aquarium system filter material comprises the following steps: respectively soaking activated carbon for an aquarium system in aqueous solutions of a catalyst and an acidifier, and drying to obtain the catalyst;
the mass ratio of the metal salt, the catalyst and the acidifying agent loaded on the activated carbon is (0.2-0.7): (0.03-0.3): (0.03-0.3).
7. A filter material as claimed in claim 6, wherein: the preparation method of the aquarium system filter material comprises the following steps:
1) preparing an acidifier with a slow-release function: the acidifier and the excipient are uniformly mixed in proportion and then uniformly embedded by the sustained-release material in proportion to prepare the acidifier with the sustained-release function, wherein the acidifier: excipient: the mass ratio of the slow-release material is 1: (0.1-0.5): (0.3-1), wherein the excipient is silicon dioxide or porous ceramsite;
2) grinding activated carbon, catalyst and acidifying agent with slow release function for aquarium system, mixing, binding the components with binder, and making into granule;
the mass ratio of the active carbon, the metal salt, the catalyst, the acidifying agent with the slow release function and the adhesive used for the aquatic system in the filter material is (0.2-0.5): (0.2-0.6): (0.03-0.1): (0.02-0.1): (0.02-0.1).
8. Use of a filter material according to any one of claims 1 to 7 in the in situ treatment of a body of water in an aquarium culture system.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132653A (en) * | 1994-12-30 | 1996-10-09 | 西村勤 | Water circulating filter method and apparatus |
| CN1986434A (en) * | 2006-12-18 | 2007-06-27 | 南京工业大学 | Granular electrode catalyst stuffing for 3D electrode reactor and its preparing method |
| CN101601998A (en) * | 2009-06-11 | 2009-12-16 | 浙江省环境保护科学设计研究院 | A kind of Preparation of catalysts method that is used for treating high-concentration organic wastewater through catalytic oxidation |
| CN101780412A (en) * | 2010-02-12 | 2010-07-21 | 新奥科技发展有限公司 | Catalyst for treating industrial waste water under normal temperature and normal pressure and preparation method thereof |
| CN202343012U (en) * | 2010-10-21 | 2012-07-25 | 陈立峰 | Filter material with pesticide and heavy metal decomposing, sterilizing and deodorizing functions |
| CN105692832A (en) * | 2016-02-26 | 2016-06-22 | 潍坊友容实业有限公司 | Purifying agent for breeding-water-quality flocculation of saline and alkaline land |
-
2018
- 2018-10-11 CN CN201811212302.XA patent/CN109381921B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132653A (en) * | 1994-12-30 | 1996-10-09 | 西村勤 | Water circulating filter method and apparatus |
| CN1986434A (en) * | 2006-12-18 | 2007-06-27 | 南京工业大学 | Granular electrode catalyst stuffing for 3D electrode reactor and its preparing method |
| CN101601998A (en) * | 2009-06-11 | 2009-12-16 | 浙江省环境保护科学设计研究院 | A kind of Preparation of catalysts method that is used for treating high-concentration organic wastewater through catalytic oxidation |
| CN101780412A (en) * | 2010-02-12 | 2010-07-21 | 新奥科技发展有限公司 | Catalyst for treating industrial waste water under normal temperature and normal pressure and preparation method thereof |
| CN202343012U (en) * | 2010-10-21 | 2012-07-25 | 陈立峰 | Filter material with pesticide and heavy metal decomposing, sterilizing and deodorizing functions |
| CN105692832A (en) * | 2016-02-26 | 2016-06-22 | 潍坊友容实业有限公司 | Purifying agent for breeding-water-quality flocculation of saline and alkaline land |
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