Composite metal calcium phosphate antibacterial agent, preparation method thereof and inorganic artificial stone thereof
阅读说明：本技术 复合金属磷酸钙抗菌剂及其制备方法、及其无机人造石 (Composite metal calcium phosphate antibacterial agent, preparation method thereof and inorganic artificial stone thereof ) 是由 高忠麟 舒诚 于 2020-08-12 设计创作，主要内容包括：本发明公开了一种复合金属磷酸钙抗菌剂及其制备、及其无机人造石。所述复合金属磷酸钙抗菌剂包括纳米磷酸钙、银原子和铜原子；所述纳米磷酸钙以改性纳米碳酸钙为原料制得；所述纳米磷酸钙的表面吸附有银原子和铜原子胶体；所述银原子作为活化剂,所述铜原子作为待激活抗菌剂。本发明所述的复合金属磷酸钙抗菌剂,含有多种的杀菌抗菌物质,具有良好的广谱杀菌效果,且不易流失。以纳米碳酸钙为原料制备的复合金属磷酸钙抗菌剂,具有非常优越的成本优势,适用于大规模的工业制造,且具有更环保和健康的优点。制得的无机人造石,抗菌效果良好,符合JC/T897－2014《抗菌陶瓷制品抗菌性能》标准的要求。(The invention discloses a composite metal calcium phosphate antibacterial agent, a preparation method thereof and an inorganic artificial stone thereof. The composite metal calcium phosphate antibacterial agent comprises nano calcium phosphate, silver atoms and copper atoms; the nano calcium phosphate is prepared by taking modified nano calcium carbonate as a raw material; silver atom and copper atom colloids are adsorbed on the surface of the nano calcium phosphate; the silver atom acts as an activator and the copper atom acts as an antimicrobial agent to be activated. The composite metal calcium phosphate antibacterial agent contains various antibacterial substances, has a good broad-spectrum antibacterial effect, and is not easy to run off. The composite metal calcium phosphate antibacterial agent prepared by taking the nano calcium carbonate as the raw material has the advantages of very superior cost advantage, suitability for large-scale industrial manufacture and more environmental protection and health. The prepared inorganic artificial stone has good antibacterial effect and meets the standard requirement of JC/T897-2014 antibacterial ceramic product antibacterial performance.)
1. The composite metal calcium phosphate antibacterial agent is characterized by comprising nano calcium phosphate, silver atoms and copper atoms; the nano calcium phosphate is prepared by taking modified nano calcium carbonate as a raw material; silver atom and copper atom colloids are adsorbed on the surface of the nano calcium phosphate; the silver atom acts as an activator and the copper atom acts as an antimicrobial agent to be activated.
2. The composite metal calcium phosphate 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 nano calcium phosphate, and the zinc oxide is used for delaying silver oxide alkalization in an alkaline environment and avoiding silver oxide from being converted into silver hydroxide first to be separated out, so that copper atoms cannot be converted into copper ions.
3. The composite metal calcium phosphate antibacterial agent according to claim 2, wherein the molar contents of copper atoms, zinc oxide and silver atoms adsorbed to the nano calcium phosphate are all decreased in this order.
4. The composite metal calcium phosphate antibacterial agent according to claim 2, wherein the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed to the nano calcium phosphate is 4:2: 1.
5. The method for preparing a composite metal calcium phosphate antibacterial agent according to any one of claims 1 to 4, comprising the following specific steps:
s1) preparing an aqueous solution containing nano calcium carbonate, heating, stirring and heating to a specified temperature, and keeping the constant temperature to prepare a nano calcium carbonate suspension;
s2) adding the surface active agent titanate into the stirred absolute ethyl alcohol until the surface active agent titanate is completely dissolved to prepare titanate solution;
s3), dripping the titanate solution into the nano calcium carbonate suspension while stirring, and continuously stirring for 1 hour to obtain a modified nano calcium carbonate solution;
s4), adding phosphoric acid into the modified nano calcium carbonate solution while stirring, and continuously stirring for 30 minutes to obtain a nano calcium phosphate solution;
s5) adding silver nitrate, copper nitrate and zinc oxide into the nano calcium phosphate solution, stirring and mixing uniformly, continuing stirring for 30 minutes, and gradually dripping a silver precipitator calcium chloride aqueous solution to prepare a composite metal colloid calcium phosphate solution;
s6) filtering the composite metal colloid calcium phosphate solution, cleaning, putting into a reduction sintering furnace, heating and roasting;
s7) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain composite metal colloid calcium phosphate baking powder;
s8) grinding and sieving the composite metal colloid calcium phosphate baking powder to obtain the composite metal calcium phosphate antibacterial agent.
6. The method for preparing a composite metal calcium phosphate antibacterial agent according to claim 5, wherein in the step S1, the molar ratio of the nano calcium carbonate to the water is 1:5, and the constant temperature is 85 ℃; in the step S2, the stirring speed is 150r/min, and the molar ratio of the absolute ethyl alcohol to the titanate is 2: 0.1; in the step S3, the molar ratio of the titanate to the nano calcium carbonate is 0.1: 1; in the step S4, the molar ratio of the phosphoric acid to the nano calcium carbonate is 2: 3.
7. The method for preparing a composite metal calcium phosphate antibacterial agent according to claim 5, wherein in step S5, the silver copper zinc nitric acid solution contains copper nitrate, zinc oxide, silver nitrate and nano calcium phosphate in a mixed molar ratio of 2.5:1:0.5: 16; the molar ratio of the calcium chloride to the silver nitrate solution is 1: 2.
8. The method for preparing a composite metal calcium phosphate antibacterial agent according to claim 5, wherein in the step S6, the roasting temperature is 1100-1180 ℃, and the roasting time is 2-3 hours; in the step S7, the pressure of adding the carbon monoxide is 0.1-0.15MPa, and the time of the reduction reaction is 0.8-1 hour; in the step S8, the mesh size of the sieved mesh is 300 mesh.
9. An inorganic artificial stone, wherein a raw material comprises an antibacterial bonding liquid, a raw material component of the antibacterial bonding liquid comprises the composite metal calcium phosphate antibacterial agent according to 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 composite metal calcium phosphate antibacterial agent is 1-3% by mass of the total mass of the inorganic artificial stone; the raw material components of the antibacterial bonding liquid also comprise water, and the antibacterial bonding liquid is a pre-prepared mixed liquid added before the inorganic artificial stone.
Technical Field
The invention relates to the technical field of antibacterial agents and artificial stones, in particular to a composite metal calcium phosphate antibacterial agent, a preparation method thereof and an inorganic artificial stone thereof.
Background
Disclosure of Invention
The invention provides a composite metal calcium phosphate 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 composite metal calcium phosphate antibacterial agent comprises nanometer calcium phosphate, silver atoms and copper atoms; the nano calcium phosphate is prepared by taking modified nano calcium carbonate as a raw material; silver atom and copper atom colloids are adsorbed on the surface of the nano calcium phosphate; the silver atom acts as an activator and the copper atom acts as an antimicrobial agent to be activated.
Preferably, the corrosion inhibitor further comprises zinc oxide, wherein the zinc oxide is a stabilizer, the zinc oxide is a colloid adsorbed on nano calcium phosphate, and the zinc oxide is used for delaying silver oxide from being alkalized in an alkaline environment, so that the situation that silver oxide is converted into silver hydroxide firstly and separated out, and copper atoms cannot be converted into copper ions is avoided.
Preferably, the molar contents of copper atoms, zinc oxide and silver atoms adsorbed to the nano calcium phosphate are all reduced in sequence.
Preferably, the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed to the nano calcium phosphate is 4:2: 1.
Further, the invention also provides a preparation method of the composite metal calcium phosphate antibacterial agent, which comprises the following specific steps:
s1) preparing an aqueous solution containing nano calcium carbonate, heating, stirring and heating to a specified temperature, and keeping the constant temperature to prepare a nano calcium carbonate suspension;
s2) adding the surface active agent titanate into the stirred absolute ethyl alcohol until the surface active agent titanate is completely dissolved to prepare titanate solution;
s3), dripping the titanate solution into the nano calcium carbonate suspension while stirring, and continuously stirring for 1 hour to obtain a modified nano calcium carbonate solution;
s4), adding phosphoric acid into the modified nano calcium carbonate solution while stirring, and continuously stirring for 30 minutes to obtain a nano calcium phosphate solution;
s5) adding silver nitrate, copper nitrate and zinc oxide into the nano calcium phosphate solution, stirring and mixing uniformly, continuing stirring for 30 minutes, and gradually dripping a silver precipitator calcium chloride aqueous solution to prepare a composite metal colloid calcium phosphate solution;
s6) filtering the composite metal colloid calcium phosphate solution, cleaning, putting into a reduction sintering furnace, heating and roasting;
s7) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain composite metal colloid calcium phosphate baking powder;
s8) grinding and sieving the composite metal colloid calcium phosphate baking powder to obtain the composite metal calcium phosphate antibacterial agent.
Further, in the step S1, the molar ratio of the nano calcium carbonate to the water is 1:5, and the constant temperature is 85 ℃; in the step S2, the stirring speed is 150r/min, and the molar ratio of the absolute ethyl alcohol to the titanate is 2: 0.1; in the step S3, the molar ratio of the titanate to the nano calcium carbonate is 0.1: 1; in the step S4, the molar ratio of the phosphoric acid to the nano calcium carbonate is 2: 3.
Further, in the step S5, the silver copper zinc nitric acid solution contains copper nitrate, zinc oxide, silver nitrate and nano calcium phosphate in a mixing molar ratio of 2.5:1:0.5: 16; the molar ratio of the calcium chloride to the silver nitrate solution is 1: 2.
Further, in the step S6, the roasting temperature is 1100-1180 ℃, and the roasting time is 2-3 hours; in the step S7, the pressure of adding the carbon monoxide is 0.1-0.15MPa, and the time of the reduction reaction is 0.8-1 hour; in the step S8, the mesh size of the sieved mesh is 300 mesh.
The invention also provides an inorganic artificial stone, which comprises the raw materials of the antibacterial bonding liquid, wherein the raw materials of the antibacterial bonding liquid comprise the composite metal calcium phosphate 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 composite metal calcium phosphate antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone; the raw material components of the antibacterial bonding liquid also comprise water, and the antibacterial bonding liquid is a pre-prepared mixed liquid added before the inorganic artificial stone.
The invention has the beneficial effects that:
the composite metal calcium phosphate antibacterial agent is nano silver-loaded calcium phosphate loaded with silver, copper metal colloid and zinc oxide, and has the characteristics of good heat resistance, high-efficiency broad-spectrum antibacterial property, excellent slow release property and the like. The nano calcium carbonate, the zinc oxide and the copper nitrate are wide in raw material source and low in purchase cost, so that the composite metal calcium phosphate antibacterial agent has better cost advantage and more optimized slow release performance compared with the silver ion-loaded antibacterial agent in the prior art.
Compared with the antibacterial agent in the prior art, the composite metal calcium phosphate antibacterial agent has the advantages that antibacterial substances are not easy to lose, the broad-spectrum sterilization effect is good, the cost advantage is superior, and the cost optimization requirement of large-scale industrial production can be met.
The invention provides a preparation method of the composite metal calcium phosphate antibacterial agent, and the prepared inorganic antibacterial agent containing the double-carrier structure and multiple antibacterial substances is convenient to store and use.
The invention also provides an inorganic artificial stone using the composite metal calcium phosphate 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 composite metal calcium phosphate antibacterial agent comprises nanometer calcium phosphate, silver atoms and copper atoms; the nano calcium phosphate is prepared by taking modified nano calcium carbonate as a raw material; silver atom and copper atom colloids are adsorbed on the surface of the nano calcium phosphate; the silver atom acts as an activator and the copper atom acts as an antimicrobial agent to be activated.
The nanometer calcium phosphate can release active silver atoms and copper atoms, and metal atom colloid is less prone to being damped and lost than metal ion colloid, so that the slow release effective period of the antibacterial substance 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; silver ion/silver electricity in the presence of silver atoms, silver ions and copper atomsThe electrode potential is 0.80 volt, the electrode potential of copper ion/copper is 0.34 volt, and due to the potential difference of the electrode potential, silver ions in the metal colloid can oxidize copper atoms in the colloid into colloidal copper ions, while silver ions are reduced into silver atoms, whose chemical reaction formula is 2Ag++Cu＝2Ag+Cu++Potential difference E thereof0＝ψ(Ag+/Ag-ψCu++0.80-0.34-0.46V, and converting the copper atom in colloid into Cu with antibacterial and bactericidal 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 composite metal calcium phosphate antibacterial agent is activated. The dried composite metal calcium phosphate antibacterial agent has good stability, and antibacterial active substances are not easy to run off.
Calcium phosphate is a main component of biological bones, has biocompatibility, and is introduced into artificial bone materials by the medical field. It is a material carrier meeting the human health standard because it has no harm to human body. The nano calcium phosphate has a porous structure, large specific surface area, strong adsorption capacity, good chemical stability and high temperature resistance, can be used as a carrier to adsorb various antibacterial metal ions, has good binding force between calcium phosphate carrier molecules and the antibacterial metal ions, and has certain dissolution property, so that the antibacterial metal ions have good bactericidal antibacterial sustained-release effect.
The nano calcium phosphate has high temperature resistance and stability, a precursor containing an antibacterial substance can be prepared by a method of wrapping and coprecipitating a phosphoric acid solution, a nano calcium carbonate microemulsion suspension and an antibacterial metal ion salt solution, then the precursor is baked at high temperature to decompose the precursor, and metal ions are oxidized into metal oxides, so that the antibacterial metal ions are stably kept in crystal lattices of calcium phosphate microcrystal particles, the calcium phosphate has weak solubility in the presence of a water-containing solution, and the separated antibacterial metal ions can complete the antibacterial function and have good slow release characteristics.
The composite metal calcium phosphate antibacterial agent contains various antibacterial substances, has a good broad-spectrum antibacterial effect, and is not easy to run off. The nano calcium phosphate prepared by using the nano calcium carbonate as the raw material has the advantages of excellent cost advantage, suitability for large-scale industrial manufacture and environmental protection and health.
Preferably, the corrosion inhibitor further comprises zinc oxide, wherein the zinc oxide is a stabilizer, the zinc oxide is a colloid adsorbed on nano calcium phosphate, and the zinc oxide is used for delaying silver oxide from being alkalized in an alkaline environment, so that the situation that silver oxide is converted into silver hydroxide firstly and separated out, and copper atoms cannot be converted into copper ions is avoided.
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 composite metal calcium phosphate antibacterial agent, so that the composite metal calcium phosphate antibacterial agent has better stability and is not easy to lose, 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 composite metal calcium phosphate 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 composite metal calcium phosphate 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.
Therefore, the antibacterial organic artificial stone with the composite metal colloid has the performance of avoiding silver precipitation and discoloration, and the product can have better color or transparent effect.
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 composite metal calcium phosphate antibacterial agent can be improved, and the alkaline application range of the composite metal calcium phosphate antibacterial agent can be widened by increasing the using amount and the proportion of the zinc oxide.
Preferably, the molar contents of copper atoms, zinc oxide and silver atoms adsorbed to the nano calcium phosphate are all reduced in sequence.
The composite metal calcium phosphate antibacterial agent contains silver atoms in an 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 use amount of silver nitrate in the raw materials is reduced, and the use amounts of copper nitrate and zinc oxide are increased, so that the cost advantage of the composite metal calcium phosphate antibacterial agent can be effectively improved, and the composite metal calcium phosphate antibacterial agent is more environment-friendly.
Preferably, the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed to the nano calcium phosphate is 4:2: 1.
The molar content ratio of the copper atoms, the zinc oxide and the silver atoms adsorbed by the silver-loaded calcium phosphate is 4:2:1, so that the cost performance is better, the composite metal calcium phosphate antibacterial agent has a good antibacterial effect, and a 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 the copper atoms adsorbed by the silver-loaded calcium phosphate into copper ions can be improved, and the stability of the antibacterial performance of the composite metal calcium phosphate antibacterial agent can be ensured.
Further, the invention also provides a preparation method of the composite metal calcium phosphate antibacterial agent, which comprises the following specific steps:
s1) preparing an aqueous solution containing nano calcium carbonate, heating, stirring and heating to a specified temperature, and keeping the constant temperature to prepare a nano calcium carbonate suspension;
s2) adding the surface active agent titanate into the stirred absolute ethyl alcohol until the surface active agent titanate is completely dissolved to prepare titanate solution;
s3), dripping the titanate solution into the nano calcium carbonate suspension while stirring, and continuously stirring for 1 hour to obtain a modified nano calcium carbonate solution;
s4), adding phosphoric acid into the modified nano calcium carbonate solution while stirring, and continuously stirring for 30 minutes to obtain a nano calcium phosphate solution;
s5) adding silver nitrate, copper nitrate and zinc oxide into the nano calcium phosphate solution, stirring and mixing uniformly, continuing stirring for 30 minutes, and gradually dripping a silver precipitator calcium chloride aqueous solution to prepare a composite metal colloid calcium phosphate solution;
s6) filtering the composite metal colloid calcium phosphate solution, cleaning, putting into a reduction sintering furnace, heating and roasting;
s7) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain composite metal colloid calcium phosphate baking powder;
s8) grinding and sieving the composite metal colloid calcium phosphate baking powder to obtain the composite metal calcium phosphate antibacterial agent.
The steps S1, S2 and S3 are used for modifying the nano calcium carbonate micro powder. The nanometer calcium carbonate has a particle size of 15-40nm and a specific surface area of more than 200m2The surface energy is high, the polarity is strong, and the agglomeration is easy to occur. The surface of the nano calcium carbonate has hydrophilic and oleophobic properties, and naturally settles under the influence of gravity in an aqueous solution, and can not be naturally suspended in water to form a suspension. Modified nano calcium carbonate with non-polar hydrophobic film on its surface and water between the particles of nano calcium carbonateThe fixed repulsion can keep a certain distance between the nano calcium carbonate particles in water, avoid the agglomeration phenomenon of the generated nano calcium carbonate particles, and prevent the nano calcium carbonate particles from floating and sinking in the water to form nano calcium carbonate suspension.
After the surface of the nano calcium carbonate particles is activated by adopting the titanate surfactant, the surface of the nano calcium carbonate particles can realize non-polar transformation, the activation index is gradually increased, when a monolayer coating state is formed, the hydrophobic group faces outwards, the optimal modified dispersion effect can be obtained, the nano calcium carbonate particles have hydrophobicity, and the dispersed nano calcium carbonate suspension aqueous solution is obtained.
The nano calcium carbonate is converted into nano calcium phosphate by adding phosphoric acid in step S4.
Adding silver nitrate, copper nitrate and zinc oxide into a nano calcium phosphate aqueous solution, adsorbing for 30 minutes, then dripping a silver precipitator calcium chloride aqueous solution into the aqueous solution to enable silver nitrate to be changed into silver chloride precipitate to be adsorbed on the surface of the nano calcium phosphate, forming a filtered coprecipitate with the nano calcium phosphate, and drying at a high temperature to form the nano calcium phosphate adsorbed with the silver oxide, the zinc oxide and the copper oxide.
The nano calcium phosphate has high temperature resistance stability, and after the nano calcium phosphate is adsorbed by the antibacterial metal ion salt solution at normal temperature, the adsorbed antibacterial metal ions are oxidized into metal oxides by high-temperature roasting, so that the binding force of the antibacterial metal oxides in the nano calcium phosphate is enhanced, the metal ions are further reduced into metal atoms, the dissociated antibacterial metal atoms are controlled, the antibacterial metal elements in the carrier are ensured to generate a good slow release effect, and the nano calcium phosphate has a long-term antibacterial effect.
Ag adsorbed to nano calcium phosphate+、Cu++And Zn++Ionic, Ag after high temperature roasting+、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 atom colloid and copper atom colloid by carbon monoxide at a high temperature of more than 1000 ℃, and the zinc oxide can not be used for carbon monoxide to be coatedThe reduction is still adsorbed on the surface of nano calcium phosphate in a colloid form, and the colloid of silver and copper atoms and the colloid of zinc oxide are adsorbed on the surface of nano calcium phosphate to form the nano calcium phosphate with antibacterial activity.
Common zinc oxide powder is dissolved into Zn++The ions are oxidized again to oxidize the zinc, and the formed colloid is adsorbed on the zinc oxide on the surface of the silver-loaded calcium phosphate, so that the silver-loaded calcium phosphate has broad-spectrum antibacterial performance and has good antibacterial effect on candida albicans.
The zinc oxide adopts zinc oxide powder, the copper oxide adopts copper nitrate powder, the raw material source is wide, and the purchase cost is low.
Therefore, the composite metal calcium phosphate antibacterial agent is nano calcium phosphate loaded with silver atom, copper atom colloid and zinc oxide colloid, and has the characteristics of good heat resistance, high-efficiency broad-spectrum antibacterial property, excellent slow release property, ultraviolet ray reinforced sterilization and the like. Compared with the silver-loaded zirconium hydroxy phosphate antibacterial agent, the composite metal calcium phosphate antibacterial agent has better cost advantage.
Further, in the step S1, the molar ratio of the nano calcium carbonate to the water is 1:5, and the constant temperature is 85 ℃; in the step S2, the stirring speed is 150r/min, and the molar ratio of the absolute ethyl alcohol to the titanate is 2: 0.1; in the step S3, the molar ratio of the titanate to the nano calcium carbonate is 0.1: 1; in the step S4, the molar ratio of the phosphoric acid to the nano calcium carbonate is 2: 3.
In the step S1, the molar ratio of the nano calcium carbonate to the water is 1:5, and the constant temperature is 85 ℃; in the step S2, the stirring speed is 150r/min, the molar ratio of the absolute ethyl alcohol to the titanate is 2:0.1, the modification effect of the nano calcium carbonate can be improved, and the dispersibility of the nano calcium carbonate and the stability of the suspension thereof can be improved. The molar ratio of the phosphoric acid to the nano calcium carbonate in the step S4 is 2:3, and the equivalent concentration of the phosphoric acid is equal to that of the nano calcium carbonate, so that the nano calcium carbonate can be effectively converted into the nano calcium phosphate.
Further, in the step S5, the silver copper zinc nitric acid solution contains copper nitrate, zinc oxide, silver nitrate and nano calcium phosphate in a mixing molar ratio of 2.5:1:0.5: 16; the molar ratio of the calcium chloride to the silver nitrate solution is 1: 2.
The molar ratio of copper nitrate to zinc oxide to silver nitrate to nano calcium phosphate is 2.5:1:0.5:16, the total content of the silver-copper-zinc ion antibacterial active substance is high, and the adsorption efficiency of zirconium hydroxy phosphate can be improved.
The molar ratio of the calcium chloride to the silver nitrate solution is 1:2, and the equivalent concentration of chloride ions contained in the calcium chloride is the same as that of silver ions contained in the silver-copper-zinc-nitric acid solution, so that the effective rate of precipitation and adsorption of the silver ions can be ensured.
Further, in the step S6, the roasting temperature is 1100-1180 ℃, and the roasting time is 2-3 hours; in the step S7, the pressure of adding the carbon monoxide is 0.1-0.15MPa, and the time of the reduction reaction is 0.8-1 hour; in the step S8, the mesh size of the sieved mesh is 300 mesh.
The roasting temperature is 1100-1180 ℃, is higher than 900 ℃ and is maintained for 2-3 hours, so that the adsorption strength of silver atoms adsorbed on the nano calcium phosphate can be improved, the loss of the silver atoms is reduced, and the stability of the composite metal calcium phosphate antibacterial agent is improved.
The pressure of the added carbon monoxide is lower than 0.1MPa, so that the reduction efficiency of the silver oxide and the copper oxide is reduced, and resources are wasted when the pressure is higher than 0.15 MPa. The reducing gas can also adopt hydrogen, and carbon monoxide is more convenient and lower in cost than hydrogen, so that the method has better economic benefit.
The smaller the particle size of the nano calcium phosphate is, the larger the surface area ratio of the nano calcium phosphate is, the higher the activity of the loaded silver-copper colloid is, the particle size of the conventional nano calcium phosphate is less than 40 nanometers, and the bonded composite metal calcium phosphate antibacterial agent with overlarge particle size can be removed by filtering with a 300-mesh filter screen, so that the bad appearance of particles with uneven distribution is avoided when the antibacterial agent is used.
The dried composite metal calcium phosphate antibacterial agent has good antibacterial effect and is convenient to store and use.
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 composite metal calcium phosphate 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 composite metal calcium phosphate antibacterial agent included in the antibacterial bonding liquid is uniformly distributed in the inorganic artificial stone and bonded 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 composite metal calcium phosphate antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone; the raw material components of the antibacterial bonding liquid also comprise water, and the antibacterial bonding liquid is a pre-prepared mixed liquid added before the inorganic artificial stone.
The inorganic artificial stone containing 1-3% of the composite metal calcium phosphate antibacterial agent can meet the requirements of JC/T897-2014 'antibacterial ceramic product antibacterial performance' standard through detection on antibacterial performance and antibacterial durability. The content of the composite metal calcium phosphate antibacterial agent contained in the inorganic artificial stone is lower than 1%, and the antibacterial performance index does not reach the standard; the content of the composite metal calcium phosphate 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, then the prefabricated material of the inorganic artificial stone is added, 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 composite metal calcium phosphate antibacterial agent is influenced.