CN111887259A - Metal colloid active carbon antibacterial agent, preparation method thereof and inorganic artificial stone thereof - Google Patents

Metal colloid active carbon antibacterial agent, preparation method thereof and inorganic artificial stone thereof Download PDF

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Publication number
CN111887259A
CN111887259A CN202010809261.3A CN202010809261A CN111887259A CN 111887259 A CN111887259 A CN 111887259A CN 202010809261 A CN202010809261 A CN 202010809261A CN 111887259 A CN111887259 A CN 111887259A
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activated carbon
antibacterial
silver
copper
metal colloid
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高忠麟
舒诚
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Best Cheer Xiamen Stone Works Co ltd
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Best Cheer Xiamen Stone Works Co ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/67—Biocides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/67—Biocides
    • C04B2103/69—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/2092—Resistance against biological degradation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/54—Substitutes for natural stone, artistic materials or the like
    • C04B2111/542—Artificial natural stone

Abstract

The invention discloses a metal colloid active carbon antibacterial agent, a preparation method thereof and an inorganic artificial stone thereof. The metal colloid active carbon antibacterial agent comprises active carbon micro powder, silver atoms and copper atoms, wherein the silver atoms are used as an activating agent, and the copper atoms are used as an antibacterial agent to be activated; the silver atoms and the copper atoms are all colloids adsorbed on the activated carbon micro powder. Under oxygen-containing humid environment, the silver atoms are oxidized into silver ions, and the copper atoms are oxidized into copper ions with antibacterial activity. The dried metal colloid active carbon antibacterial agent has good stability, and antibacterial active substances are not easy to run off. The invention also provides a preparation method of the metal colloid activated carbon antibacterial agent, and an inorganic artificial stone using the metal colloid activated carbon antibacterial agent, which have the characteristics of good heat resistance, broad-spectrum antibacterial property, excellent slow release property, low purchase cost and the like, and have better cost advantage.

Description

Metal colloid active carbon antibacterial agent, preparation method thereof and inorganic artificial stone thereof
Technical Field
The invention relates to the technical field of antibacterial agents and artificial stones, in particular to a metal colloid activated carbon antibacterial agent, a preparation method thereof and an inorganic artificial stone thereof.
Background
Activated carbon has been widely used in conventional treatment and advanced treatment of water, and has been widely used in the fields of decontamination, harmful gas adsorption and poison prevention due to its super strong adsorption capacity.
Silver has long been found to have bactericidal properties and, with scientific progress, colloidal silver (particles of size between 10 and 100 nm) has been found to be effective against over 650 different infectious diseases.
The active carbon loaded with silver ions in the prior art generally adopts a physical adsorption process. The technical scheme does not change the structure of silver nitrate, and the active carbon powder can be quickly lost when meeting soluble liquid, so that the slow release property is poor. Silver nitrate is also converted into silver chloride to reduce silver ion loss, but the compatibility of silver chloride is poor, and the sterilization and antibacterial capabilities of silver chloride are greatly weakened.
Moreover, most of the raw material sources of silver ions are silver nitrate, so the purchase cost is high. And the silver nitrate belongs to strong oxidants, corrosive products and environmental pollutants, so that the use amount of the silver nitrate is reduced, and the method is more environment-friendly.
Therefore, the development of other raw materials capable of replacing silver ions and preparing the antibacterial agent which has good antibacterial effect and is not easy to lose is of great significance.
Disclosure of Invention
The invention provides a metal colloid active carbon antibacterial agent, a preparation method thereof and an inorganic artificial stone thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a metal colloid active carbon antibacterial agent comprises active carbon micro powder, silver atoms and copper atoms, wherein the silver atoms are used as an activating agent, and the copper atoms are used as an antibacterial agent to be activated; the silver atoms and the copper atoms are all colloids adsorbed on the activated carbon micro powder.
Preferably, the silver-containing silver oxide powder further comprises zinc oxide, wherein the zinc oxide is a stabilizer, the zinc oxide is colloid adsorbed on the activated carbon micro powder, and the zinc oxide is used for delaying the alkalization of the silver oxide in an alkaline environment.
Preferably, the molar contents of copper atoms, zinc oxide and silver atoms adsorbed by the activated carbon micro powder are reduced in sequence.
Preferably, the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed by the activated carbon micro powder is 4:2: 1.
Further, the invention also provides a preparation method of the metal colloid activated carbon antibacterial agent, which comprises the following specific steps:
s1) preparing an aqueous solution containing silver nitrate, copper nitrate and zinc oxide to obtain a silver-copper-zinc-nitric acid solution;
s2) adding the activated carbon micro powder into the silver-copper-zinc-nitric acid solution, and uniformly stirring to obtain an activated carbon micro powder adsorption solution;
s3) putting the activated carbon micro powder adsorption solution into an oven for drying to prepare activated carbon micro powder adsorption dry powder;
s4) sending the active carbon micro powder adsorption dry powder into a reduction sintering furnace, vacuumizing and heating, and roasting at constant temperature;
s5) adding hydrogen into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain activated carbon micro powder adsorption baking powder;
s6) sieving the activated carbon micro powder adsorption baking powder to obtain the metal colloid activated carbon antibacterial agent.
Further, in step S1, the silver copper zinc nitric acid solution contains copper nitrate, zinc oxide, silver nitrate and water at a mixing molar ratio of 2.5:1:0.5: 20; in the step S2, the molar ratio of the silver-copper-zinc nitric acid solution to the activated carbon micro powder is 1: 4.
Further, in the step S3, the drying temperature is 100-; in the step S4, the temperature of the constant-temperature roasting is 500 ℃, and the pressure of the vacuum is 8-15 Pa.
Further, in the step S5, the pressure of the hydrogen gas is 0.08 to 0.12MPa, and the time of the reduction reaction is 0.5 to 0.8 hour; in the step S6, the mesh size of the sieved mesh is 400 mesh.
The invention further provides an inorganic artificial stone, which comprises the raw materials of an antibacterial bonding liquid, wherein the raw materials of the antibacterial bonding liquid comprise the metal colloid activated carbon antibacterial agent, the antibacterial bonding liquid is used for bonding the solid raw materials of the inorganic artificial stone, and the antibacterial bonding liquid is uniformly distributed in the inorganic artificial stone.
Further, the metal colloid activated carbon antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone; the raw material components of the antibacterial binding liquid also comprise water, and the antibacterial binding liquid is a prefabricated mixed liquid.
The invention has the beneficial effects that:
the metal colloid active carbon antibacterial agent is active carbon micro powder loaded with silver atoms and copper atoms, and zinc oxide, and has the characteristics of good heat resistance, broad-spectrum antibacterial property, excellent slow release property and the like.
The zinc oxide and the copper nitrate have wide raw material sources and low purchase cost, so that the metal colloid active carbon antibacterial agent has better cost advantage and more optimized slow release performance compared with the active carbon antibacterial agent loaded with silver ions in the prior art.
The invention provides a preparation method of the metal colloid active carbon antibacterial agent, wherein the surface of active carbon micro powder is attached with metal colloid of silver and copper and zinc oxide colloid to form the active carbon micro powder with antibacterial activity.
The invention also provides the inorganic artificial stone using the metal colloid activated carbon antibacterial agent, and the prepared inorganic artificial stone has excellent antibacterial performance and antibacterial durability.
Detailed Description
The technical solution of the present invention is further described below in specific embodiments.
A metal colloid active carbon antibacterial agent comprises active carbon micro powder, silver atoms and copper atoms, wherein the silver atoms are used as an activating agent, and the copper atoms are used as an antibacterial agent to be activated; the silver atoms and the copper atoms are all colloids adsorbed on the activated carbon micro powder.
The activated carbon has strong adsorption capacity, so that the activated carbon is widely applied to water treatment and can adsorb organic compounds, chlorine, heavy metal ions and the like in water. The active carbon can be used as an ideal carrier of the metal ions for sterilization and antibiosis by utilizing the adsorption performance of the active carbon to various metal ions, can store a large amount of metal colloids for sterilization and antibiosis, can reduce the loss of the metal colloids for sterilization and antibiosis, and improves the release concentration and the sustained release capacity of the metal ions for sterilization and antibiosis.
The silver-copper metal colloid loaded on the active carbon micro powder can release active silver atoms and copper atoms, and the metal atom colloid is less prone to being damped and lost than the metal ion colloid, so that the slow release effective period of the antibacterial agent can be prolonged.
When silver atoms are in a humid environment containing oxygen, such as contact with water, acid or alkaline solution, the silver atoms are oxidized into silver ions; when silver atoms, silver ions and copper atoms exist simultaneously, the electrode potential of the silver ions/silver atoms is 0.80 volt, the electrode potential of the copper ions/copper atoms is 0.34 volt, and due to the potential difference of the electrode potentials, the silver ions in the metal colloid can oxidize the copper atoms in the colloidThe copper ions are colloidal copper ions, and the silver ions are reduced to silver atoms, which have the chemical reaction formula of 2Ag++Cu＝2Ag+Cu++The potential difference is released E0＝ψAg+/Ag-ψCu++0.80-0.34-0.46 volt, and the copper atom in colloid is converted into Cu with bactericidal and antibacterial activity++Ions.
When in oxygen-containing humid environment, silver atoms are oxidized into silver ions, copper atoms in the silver ion oxidized colloid are colloid copper ions and are copper ions with antibacterial activity, and the antibacterial activity of the metal colloid activated carbon antibacterial agent is activated. The dried metal colloid active carbon antibacterial agent has good stability, and antibacterial active substances are not easy to run off.
The activated carbon micro powder can be commercially available activated carbon micro powder, the particle size D50 is less than or equal to 10 mu m, and the specific surface area is not less than 50m2And/g, the purity is not less than 99.9 percent.
Preferably, the silver-containing silver oxide powder further comprises zinc oxide, wherein the zinc oxide is a stabilizer, the zinc oxide is colloid adsorbed on the activated carbon micro powder, and the zinc oxide is used for delaying the alkalization of the silver oxide in an alkaline environment.
The zinc oxide is an antibacterial agent with a good antibacterial effect, has photosensitive bactericidal performance, is wide in raw material source and low in purchase cost, and has superior cost advantage compared with silver nitrate powder because silver nitrate is a raw material of silver atoms.
The silver oxide colloid is adsorbed on the metal colloid active carbon antibacterial agent, has better stability and is not easy to lose, the metal colloid active carbon antibacterial agent contains various active antibacterial substances, has wider product application range and more comprehensive antibacterial effect, and has better finished product advantages while improving the slow release performance.
The zinc oxide adsorbed on the metal colloid activated carbon antibacterial agent is used for protecting silver oxide from being alkalized in an alkaline environment and preventing the silver oxide from being separated out by being converted into silver hydroxide, so that the conversion rate of copper atoms into copper ions is reduced, and the antibacterial performance of the metal colloid activated carbon antibacterial agent is reduced. Only after the zinc oxide is consumed by the reaction, the silver oxide is alkalized and converted into silver hydroxide to be separated out.
The zinc oxide has good activity, can improve the adverse effect of precipitation under the alkaline environment of silver ions, and has the following chemical reaction mechanism.
Silver ions react with basic groups in alkaline environment to generate silver hydroxide precipitate
Ag++OH-AgOH ↓ (white)
Unstable decomposition of silver hydroxide precipitate to silver oxide precipitate
2AgOH＝Ag2O ↓ (dark brown) + H2O
When zinc oxide and silver oxide coexist, the chemical reaction activity of the zinc oxide under the alkaline environment is higher than that of the silver oxide, and the zinc oxide firstly reacts with basic groups to delay and prevent the precipitation of the silver oxide.
ZnO++2OH-＝Zn(OH)2↓ (white)
The zinc oxide is used as a stabilizer of silver ions, so that the stability of the antibacterial performance of the metal colloid activated carbon antibacterial agent can be improved, and the alkaline application range of the metal colloid activated carbon antibacterial agent can be widened by increasing the using amount and proportion of the zinc oxide.
Preferably, the molar contents of copper atoms, zinc oxide and silver atoms adsorbed by the activated carbon micro powder are reduced in sequence.
Preferably, the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed by the activated carbon micro powder is 4:2: 1.
The metal colloid active carbon antibacterial agent contains silver atoms in oxygen-containing humid environment, and can effectively convert copper atoms into copper ions. Under the condition of keeping the effect of converting copper ions of silver atoms, the using amount of silver nitrate in the raw materials is reduced, and the using amounts of copper nitrate and zinc oxide are increased, so that the cost advantage of the metal colloid activated carbon antibacterial agent can be effectively improved, and the metal colloid activated carbon antibacterial agent is more environment-friendly.
The molar content ratio of copper atoms, zinc oxide atoms and silver atoms adsorbed by the activated carbon micro powder is 4:2:1, so that the activated carbon micro powder has better cost performance, the metal colloid activated carbon antibacterial agent has good antibacterial effect, and better cost advantage can be obtained.
The molar content ratio of the zinc oxide to the silver atoms is 2:1, the probability that the silver oxide is alkalized first can be reduced, the conversion rate of converting copper atoms adsorbed by the active carbon micro powder into copper ions can be improved, and the stability of the antibacterial performance of the metal colloid active carbon antibacterial agent can be guaranteed.
Further, the invention also provides a preparation method of the metal colloid activated carbon antibacterial agent, which comprises the following specific steps:
s1) preparing an aqueous solution containing silver nitrate, copper nitrate and zinc oxide to obtain a silver-copper-zinc-nitric acid solution;
s2) adding the activated carbon micro powder into the silver-copper-zinc-nitric acid solution, and uniformly stirring to obtain an activated carbon micro powder adsorption solution;
s3) putting the activated carbon micro powder adsorption solution into an oven for drying to prepare activated carbon micro powder adsorption dry powder;
s4) sending the active carbon micro powder adsorption dry powder into a reduction sintering furnace, vacuumizing and heating, and roasting at constant temperature;
s5) adding hydrogen into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain activated carbon micro powder adsorption baking powder;
s6) sieving the activated carbon micro powder adsorption baking powder to obtain the metal colloid activated carbon antibacterial agent.
The preparation method of the metal colloid active carbon antibacterial agent comprises the steps of dipping active carbon micro powder in silver nitrate, copper nitrate and oxidized aqueous solution, wherein metal ions adsorbed on the active carbon micro powder comprise Ag+、Cu++And Zn++Ion, drying the activated carbon powder, and calcining at high temperature to obtain Ag+、Cu++And Zn++The ions are converted into silver oxide, copper oxide and zinc oxide, and then the silver oxide and the copper oxide are reduced into silver metal colloid and copper metal colloid by hydrogen under high-temperature vacuum, the zinc oxide can not be reduced by hydrogen and still can be adsorbed on the surface of the active carbon micro powder in the form of zinc oxide colloid, and the metal colloid and the zinc oxide colloid containing the silver and the copper are adsorbed on the surface of the active carbon micro powder to form the active carbon with antibacterial activityThe activated carbon fine powder of (1).
Common zinc oxide powder is dissolved into Zn++The ions are oxidized into zinc oxide, and formed colloid is adsorbed on the zinc oxide on the surface of the active carbon micro powder, so that the active carbon micro powder has broad-spectrum antibacterial performance and good antibacterial effect on candida albicans.
Therefore, the metal colloid active carbon antibacterial agent is active carbon micro powder loaded with silver, copper metal colloid and zinc oxide, and has the characteristics of good heat resistance, broad-spectrum antibacterial property, excellent slow release property and the like.
The zinc oxide powder and the copper nitrate powder have wide raw material sources and low purchase cost, and compared with the silver-loaded active carbon antibacterial agent, the metal colloid active carbon antibacterial agent has better cost advantage.
Further, in step S1, the silver copper zinc nitric acid solution contains copper nitrate, zinc oxide, silver nitrate and water at a mixing molar ratio of 2.5:1:0.5: 20; in the step S2, the molar ratio of the silver-copper-zinc nitric acid solution to the activated carbon micro powder is 1: 4.
The total content of the silver-copper-zinc antibacterial active substances reaches 25 percent, so that the adsorption efficiency of the activated carbon can be improved. The concentration of the contained antibacterial active substance is high, the molar ratio of the silver-copper-zinc nitrate solution to the active carbon micro powder is 1:4, and the metal colloid active carbon antibacterial agent has a good antibacterial effect and is convenient to store and use.
Further, in the step S3, the drying temperature is 100-; in the step S4, the temperature of the constant-temperature roasting is 500 ℃, and the pressure of the vacuum is 8-15 Pa.
The drying temperature is not lower than 100 ℃, and the moisture contained in the active carbon micro powder adsorption solution can be fully dried.
Silver nitrate and copper nitrate are roasted at high temperature to form silver oxide and copper oxide, and then the silver oxide and the copper oxide are reduced by hydrogen at high temperature under vacuum to form metal atom colloid, and the metal colloid of silver and copper atoms is gathered on the surface of the active carbon micro powder to be condensed into the active carbon micro powder with antibacterial activity.
The high-temperature heating is carried out in a vacuum state, oxygen contained in the air is removed, and the oxidation of the active carbon at high temperature can be avoided. The decomposition temperature of the silver nitrate is 440 ℃, the silver nitrate is roasted at the constant temperature of 500 ℃, the silver nitrate can be completely decomposed and oxidized into silver oxide, the decomposition temperature of the copper nitrate is lower than that of the silver nitrate, and the decomposition and oxidation of the copper nitrate are more complete.
Further, in the step S5, the pressure of the hydrogen gas is 0.08 to 0.12MPa, and the time of the reduction reaction is 0.5 to 0.8 hour; in the step S6, the mesh size of the sieved mesh is 400 mesh.
And (2) roasting at the constant temperature of 500 ℃, keeping the vacuum pressure at 8-15Pa, ensuring the reduction efficiency of the added hydrogen by vacuumizing, and reducing the reduction efficiency of the silver oxide and the copper oxide when the pressure of the added hydrogen is lower than 8Pa, so that resources are wasted when the pressure is higher than 12 Pa. The safety degree of avoiding the activated carbon from being oxidized can be further improved by adding the hydrogen. The constant temperature is 500 ℃, the temperature is higher than 440 ℃ and is maintained for 0.5 to 0.8 hour, and the reduction percentage of the silver oxide and the copper oxide reduced into silver-copper colloid can be improved.
The smaller the particle size of the active carbon micro powder is, the larger the surface area ratio of the active carbon micro powder is, the higher the activity of the carried silver-copper colloid is, the particle size of the conventional active carbon micro powder is 325 meshes, and the bonded metal colloid active carbon antibacterial agent with overlarge particle size can be removed by adopting a 400-mesh filter sieve for filtering, so that the bad appearance of particles with uneven distribution is avoided when the active carbon micro powder is used.
The invention further provides an inorganic artificial stone, which comprises the raw materials of an antibacterial bonding liquid, wherein the raw materials of the antibacterial bonding liquid comprise the metal colloid activated carbon antibacterial agent, the antibacterial bonding liquid is used for bonding the solid raw materials of the inorganic artificial stone, and the antibacterial bonding liquid is uniformly distributed in the inorganic artificial stone.
The antibacterial bonding liquid is used for bonding solid raw materials of the inorganic artificial stone and is uniformly distributed in the inorganic artificial stone. The metal colloid active carbon antibacterial agent in the antibacterial binding liquid is uniformly distributed in the inorganic artificial stone and is bound in the inorganic artificial stone, so that the antibacterial effect of the inorganic artificial stone is more stable and uniform.
The solid raw materials of the inorganic artificial stone comprise quartz stone, marble, granite, feldspar, super quartz stone and colorant.
Further, the metal colloid activated carbon antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone; the raw material components of the antibacterial binding liquid also comprise water, and the antibacterial binding liquid is a prefabricated mixed liquid.
The inorganic artificial stone containing 1-3% of the metal colloid active carbon antibacterial agent can meet the requirements of JC/T897-2014 antibacterial ceramic product antibacterial performance standard through detection of antibacterial performance and antibacterial durability. The content of the metal colloid active carbon antibacterial agent contained in the inorganic artificial stone is lower than 1 percent, and the antibacterial performance index does not reach the standard; the content of the metal colloid active carbon antibacterial agent contained in the inorganic artificial stone is higher than 3%, the antibacterial performance is excessive, and resources are wasted.
Because the main raw materials of the inorganic artificial stone in the prior art are mostly cement-series materials, the alkalinity is higher, the raw materials contain water the antibacterial bonding liquid is prepared, and then the mixture for preparing the inorganic artificial stone is added, so that the alkaline damage of the cement-series materials in the inorganic artificial stone can be avoided, the silver ions contained in the antibacterial bonding liquid are prevented from being changed into silver hydroxide, the conversion rate of copper atoms to copper ions is reduced, and the antibacterial performance of the inorganic artificial stone prepared by the metal colloid activated carbon antibacterial agent is influenced.
Examples and comparative examples
The inorganic artificial stone of each example and comparative example was prepared as follows, and commercially available activated carbon fine powder having a particle size D50 ≦ 10 μm and a specific surface area ≧ 50m was used as the activated carbon fine powder2And the purity is not less than 99.9 percent, and the silver nitrate, the copper nitrate and the zinc oxide are commercially available analytically pure powder.
The method comprises the following specific steps:
1. a metal colloid active carbon antibacterial agent comprises active carbon micro powder, silver atoms, copper atoms and zinc oxide, wherein the silver atoms, the copper atoms and the zinc oxide are colloids adsorbed on the active carbon micro powder. The molar contents of copper atoms, zinc oxide and silver atoms adsorbed by the activated carbon micro powder are sequentially reduced.
2. The molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed by the activated carbon micro powder is 4:2: 1.
3. The preparation method of the metal colloid active carbon antibacterial agent comprises the following specific steps:
s1) preparing an aqueous solution containing silver nitrate, copper nitrate and zinc oxide to obtain a silver-copper-zinc-nitric acid solution;
s2) adding the activated carbon micro powder into the silver-copper-zinc-nitric acid solution, and uniformly stirring to obtain an activated carbon micro powder adsorption solution;
s3) putting the activated carbon micro powder adsorption solution into an oven for drying to prepare activated carbon micro powder adsorption dry powder;
s4) sending the active carbon micro powder adsorption dry powder into a reduction sintering furnace, vacuumizing and heating, and roasting at constant temperature;
s5) adding hydrogen into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain activated carbon micro powder adsorption baking powder;
s6) sieving the activated carbon micro powder adsorption baking powder to obtain the metal colloid activated carbon antibacterial agent.
In the step S1, the silver-copper-zinc-nitric acid solution contains copper nitrate, zinc oxide, silver nitrate and water at a mass mixing ratio of 2.5:1:0.5: 20; in the step S2, the ratio of the silver-copper-zinc nitrate solution to the activated carbon micro powder is 1: 4; in the step S3, the drying temperature is not lower than 100 ℃; in the step S4, the constant-temperature roasting temperature is 500 ℃; the pressure of the vacuum is 8-15 Pa; in the step S5, the pressure of the hydrogen gas is 0.08-0.12MPa, and the time of the reduction reaction is 0.5-0.8 hour; in the step S6, the mesh size of the sieved mesh is 400 mesh.
4. The method comprises the following steps of preparing the inorganic artificial stone, wherein the raw materials of the inorganic artificial stone comprise antibacterial bonding liquid, the antibacterial bonding liquid contains the metal colloid activated carbon antibacterial agent, the raw material components of the antibacterial bonding liquid also comprise water, the antibacterial bonding liquid is a prefabricated mixed liquid, and the metal colloid activated carbon antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone.
5. The contents and ratios of the specific raw material components and the parameters in each example are shown in Table 1, and the contents and ratios of the specific raw material components and the parameters in each ratio are shown in Table 2.
6. The inorganic artificial stone prepared in each example and comparative example was sampled with reference to JC/T897-2014 "antibacterial property of antibacterial ceramic article" standard, and the antibacterial properties and antibacterial durability of escherichia coli, staphylococcus aureus and candida albicans were tested, and the test results of examples and base materials are shown in table 1, and the test results of comparative example are shown in table 1.
TABLE 1 data and test results for the examples and substrates
Figure BDA0002630326840000111
Figure BDA0002630326840000121
TABLE 2 comparative data and test results
Figure BDA0002630326840000122
The following is an analysis explanation based on the above cases and test results of the respective examples and comparative examples:
1. according to the standard requirement of JC/T897-2014 antibacterial ceramic product antibacterial performance, the antibacterial rate (%) of the antibacterial performance is more than or equal to 90 percent and the antibacterial rate (%) of the antibacterial durability is more than or equal to 85 percent, and the detection results of the antibacterial rates of the antibacterial performance and the antibacterial rate of the antibacterial durability of escherichia coli, staphylococcus aureus and candida albicans of the base material are unqualified.
2. Analysis of the test results of examples 1 to 5:
(1) the antibacterial properties (%) and antibacterial durability (%) of Escherichia coli, Staphylococcus aureus and Candida albicans of examples 1 to 3 were all acceptable.
(2) Example 1 differs from example 2 in that: the added copper nitrate is less in mole ratio, 2.0 mole is less than 2.5 mole, and the detection results of the antibacterial rate (%) of the antibacterial performance and the antibacterial rate (%) of the antibacterial durability performance of the enterobacteria, staphylococcus aureus and candida albicans in the example 1 are both qualified and just meet the qualified standard; therefore, the ratio of the silver-copper-zinc-nitric acid solution to the activated carbon micro powder is 1:4, the contained metal colloid activated carbon antibacterial agent accounts for 1% of the total mass of the inorganic artificial stone, and the mass mixing ratio of copper nitrate, zinc oxide, silver nitrate and water in the silver-copper-zinc-nitric acid solution is 2.5:1:0.5: 20; the inorganic artificial stones prepared from the metal colloid activated carbon antibacterial agent can be guaranteed to have better antibacterial effect; the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed by the activated carbon micro powder is 4:2:1, so that the activated carbon micro powder has a good cost performance.
(3) Example 3 differs from example 2 in that: in the embodiment 3, more copper nitrate and more zinc oxide are added, the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed by the activated carbon micro powder is 3:1.5:0.5, and the detection results of the antibacterial rate and the antibacterial durability antibacterial rate of escherichia coli, staphylococcus aureus and candida albicans in the embodiment 3 are very excellent and higher than 95%;
(4) example 4 differs from example 3 in that: the zinc oxide is not added in the embodiment 4, and the detection results of the antibacterial performance and antibacterial durability antibacterial rate of escherichia coli and staphylococcus aureus in the embodiment 4 are both very excellent and higher than 95%; but the detection results of the antibacterial performance and antibacterial durability of the candida albicans in the example 4 are not qualified; the zinc oxide has a relatively outstanding antibacterial effect on candida albicans, and the copper ions have a general antibacterial effect on candida albicans;
(5) example 5 differs from example 4 in that: in example 5, zinc oxide is not added, but the content of 0.5 mol of silver nitrate is increased, and the detection results of the antibacterial performance and antibacterial durability of candida albicans of example 5 are qualified, which indicates that the increased content of 0.5 mol of silver nitrate has a prominent antibacterial effect on candida albicans; comparing with the examples 1-5, the zinc oxide with the concentration ratio of 1 mol ratio can replace silver ions to have more outstanding antibacterial effect on candida albicans;
(6) the components and the detection results of examples 1 to 5 were comprehensively analyzed to find that: the raw material components of the antibacterial binding liquid also comprise water, and the antibacterial binding liquid is a pre-prepared mixed liquid; the metal colloid active carbon antibacterial agent is effective, and the antibacterial binding liquid and the prepared inorganic artificial stone have good antibacterial effect and good durability. The ratio of the silver-copper-zinc-nitric acid solution to the activated carbon micro powder is 1:4, the contained metal colloid activated carbon antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone, and the mass mixing ratio of copper nitrate, zinc oxide, silver nitrate and water in the silver-copper-zinc-nitric acid solution is 2.5:1:0.5: 20; the better antibacterial effect of the inorganic artificial stones prepared from the metal colloid activated carbon antibacterial agent can be ensured; the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed by the activated carbon micro powder is 4:2:1, so that the activated carbon micro powder has a good cost performance.
3. Comparative example 1 was analyzed, and compared to example 2, the difference of comparative example 1 was: the time of the reduction reaction of comparative example 1 is 0.3 hour, and the lower limit of less than 0.5 hour decreases the reduction rate of silver oxide, thus decreasing the conversion rate of copper ions of the antibacterial function, resulting in that the results of the tests of antibacterial performance antibacterial rate and antibacterial durability antibacterial rate (%) of escherichia coli, staphylococcus aureus of comparative example 1 are not good.
4. Comparative example 2 was analyzed and compared to example 2, the difference of comparative example 2 was: the molar ratio of the copper nitrate added in the comparative example 2 is 1.5, and the molar content ratio of copper atoms, zinc oxide and silver atoms which are adsorbed by the activated carbon micro powder is 4:2:1, so that the content of copper ions with the antibacterial function is reduced, and the detection results of the antibacterial performance antibacterial rate and the antibacterial durability antibacterial rate (%) of escherichia coli and staphylococcus aureus in the comparative example 2 are unqualified.
5. Comparative example 3 was analyzed, and compared to example 2, the difference of comparative example 3 was: the molar ratio of the silver nitrate added in the comparative example 3 is 1, the molar content ratio of copper atoms, zinc oxide and silver atoms higher than that of the activated carbon micro powder is 4:2:1, and the detection results of the antibacterial rate and antibacterial durability antibacterial rate (%) of escherichia coli, staphylococcus aureus and candida albicans in the comparative example 3 reach the highest limit, so that resources are wasted due to excessive quality.
6. Comparative example 4 was analyzed, and compared to example 2, comparative example 4 was different: the molar ratio of the silver nitrate added in the comparative example 4 is 0.3, the molar content ratio of copper atoms, zinc oxide and silver atoms which are lower than the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed by the activated carbon micro powder is 4:2:1, so that copper ions are not completely converted, and the detection results of the antibacterial rate of the antibacterial performance and the antibacterial rate (%) of the antibacterial durability performance of escherichia coli and staphylococcus aureus in the comparative example 4 are not qualified; therefore, the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed by the activated carbon micro powder is set to be 4:2:1, which is suitable.
7. Comparative example 5 was analyzed, and compared to example 2, the difference of comparative example 5 was: the antibacterial bonding liquid of comparative example 5 is not a pre-prepared mixed liquid, and the zinc oxide is not added, silver atoms adsorbed by the activated carbon micro powder are alkalized in an alkaline environment, the effect of copper oxide atoms as copper ions is lost, and the detection results of antibacterial performance antibacterial rate and antibacterial durability antibacterial rate (%) of escherichia coli, staphylococcus aureus and candida albicans of the prepared inorganic artificial stone are not qualified.
8. Comparative example 6 was analyzed, comparing with example 2 and comparative example 5, the difference of comparative example 6 is: although the antibacterial binding solution of comparative example 5 is not a pre-prepared mixed solution, the detection results of the antibacterial performance and antibacterial durability (%) of escherichia coli, staphylococcus aureus and candida albicans of the prepared inorganic artificial stone are all not qualified by adding the zinc oxide, but the antibacterial performance and antibacterial durability (%) of the escherichia coli, staphylococcus aureus and candida albicans of the detection results are better improved than those of comparative example 5, which shows that the zinc oxide has a specific and obvious delaying effect on basification of silver atoms in an alkaline environment and has a good stability effect on the metal colloid activated carbon antibacterial agent.
9. Comparative examples 7 and 8 were analyzed, and in comparison with example 2, comparative examples 7 and 8 differ by: the content ratios of the added antibacterial active carbon antibacterial agents are different, wherein 0.7 percent of the comparative example 7 is less than 1 percent, and 3.5 percent of the comparative example 8 is more than 3 percent; the results of the tests of the antibacterial performance and antibacterial durability (%) of comparative example 7 were all unqualified; the results of the tests of antibacterial performance and antibacterial durability (%) of comparative example 8 were all acceptable, but the improvement in comparison with example 3 was limited, and the results of the tests of antibacterial performance and antibacterial durability (%) of example 3 were all excellent, so that it was appropriate to set the percentage of the metal colloid activated carbon antibacterial agent to 1-3% of the total mass of the inorganic artificial stone.
In conclusion, the inorganic artificial stone prepared by using the metal colloid activated carbon antibacterial agent has excellent antibacterial effects on escherichia coli, staphylococcus aureus and candida albicans.
The inorganic artificial stone containing 1-3% of the metal colloid active carbon antibacterial agent has antibacterial performance and antibacterial durability which can meet the requirements of JC/T897-2014 antibacterial performance of antibacterial ceramic products.
The metal colloid active carbon antibacterial agent is active carbon micro powder loaded with silver, copper metal colloid and zinc oxide colloid, is convenient to store and not easy to run off, and has the characteristics of good heat resistance, broad-spectrum antibacterial property, good slow release property and the like.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.

Claims (10)

1. The metal colloid activated carbon antibacterial agent is characterized by comprising activated carbon micro powder, silver atoms and copper atoms, wherein the silver atoms are used as an activating agent, and the copper atoms are used as an antibacterial agent to be activated; the silver atoms and the copper atoms are all colloids adsorbed on the activated carbon micro powder.
2. The metal colloid activated carbon antibacterial agent according to claim 1, further comprising zinc oxide, wherein the zinc oxide is a stabilizer, the zinc oxide is a colloid adsorbed on the activated carbon fine powder, and the zinc oxide is used for delaying silver oxide alkalization in an alkaline environment.
3. The metal colloid activated carbon antibacterial agent according to claim 2, wherein the molar contents of copper atoms, zinc oxide and silver atoms adsorbed by the fine activated carbon powder are sequentially decreased.
4. The metal colloid activated carbon antibacterial agent according to claim 2, wherein the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed by the fine activated carbon powder is 4:2: 1.
5. The method for preparing a metal colloid activated carbon antibacterial agent according to any one of claims 1 to 4, characterized by comprising the following specific steps:
s1) preparing an aqueous solution containing silver nitrate, copper nitrate and zinc oxide to obtain a silver-copper-zinc-nitric acid solution;
s2) adding the activated carbon micro powder into the silver-copper-zinc-nitric acid solution, and uniformly stirring to obtain an activated carbon micro powder adsorption solution;
s3) putting the activated carbon micro powder adsorption solution into an oven for drying to prepare activated carbon micro powder adsorption dry powder;
s4) sending the active carbon micro powder adsorption dry powder into a reduction sintering furnace, vacuumizing and heating, and roasting at constant temperature;
s5) adding hydrogen into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain activated carbon micro powder adsorption baking powder;
s6) sieving the activated carbon micro powder adsorption baking powder to obtain the metal colloid activated carbon antibacterial agent.
6. The method of claim 5, wherein in step S1, the silver-copper-zinc nitric acid solution contains copper nitrate, zinc oxide, silver nitrate and water at a mixing molar ratio of 2.5:1:0.5: 20; in the step S2, the molar ratio of the silver-copper-zinc nitric acid solution to the activated carbon micro powder is 1: 4.
7. The method as claimed in claim 5, wherein the drying temperature is 100-120 ℃ in the step S3; in the step S4, the temperature of the constant-temperature roasting is 500 ℃, and the pressure of the vacuum is 8-15 Pa.
8. The method of claim 5, wherein in step S5, the pressure of hydrogen gas is 0.08-0.12MPa, and the time of the reduction reaction is 0.5-0.8 hr; in the step S6, the mesh size of the sieved mesh is 400 mesh.
9. An inorganic artificial stone, characterized in that raw materials comprise an antibacterial bonding liquid, the raw material components of the antibacterial bonding liquid comprise the metal colloid activated carbon antibacterial agent of any one of claims 1 to 4, the antibacterial bonding liquid is used for bonding solid raw materials of the inorganic artificial stone, and the antibacterial bonding liquid is uniformly distributed in the inorganic artificial stone.
10. The inorganic artificial stone according to claim 9, wherein the metal colloid activated carbon antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone; the raw material components of the antibacterial binding liquid also comprise water, and the antibacterial binding liquid is a prefabricated mixed liquid.
CN202010809261.3A 2020-08-12 2020-08-12 Metal colloid active carbon antibacterial agent, preparation method thereof and inorganic artificial stone thereof Pending CN111887259A (en)

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