CN1653908A - Method for preparing superfine composite inorganic antimicrobial agent - Google Patents

Method for preparing superfine composite inorganic antimicrobial agent Download PDF

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Publication number
CN1653908A
CN1653908A CN 200510041626 CN200510041626A CN1653908A CN 1653908 A CN1653908 A CN 1653908A CN 200510041626 CN200510041626 CN 200510041626 CN 200510041626 A CN200510041626 A CN 200510041626A CN 1653908 A CN1653908 A CN 1653908A
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preparation
antimicrobial agent
inorganic antimicrobial
composite inorganic
superfine composite
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CN 200510041626
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CN1310589C (en
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黄岳元
仪建华
郭人民
谢建榕
米钰
王亚平
祖庸
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Northwest University
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Northwest University
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Abstract

The present invention is preparation process of superfine compound inorganic antibiotic. Technologically, the present invention is that silver ion as depositing crystal nucleus is coated with titanium or other metal ion obtained with urea as precipitant and phosphate as secondary coating, and re-compounded with surfactant, and through dewatering, drying, calcining at 700-1100 for 2-10 hr, superfine antibiotic powder is prepared. The prepared antibiotic powder has relatively high bacteria and fungi killing effect, is superior to available silver antibiotic and titanium antibiotic, and may be used widely in fabric, plastic, paint, enamel, water processing and other fields.

Description

A kind of preparation method of superfine composite inorganic antimicrobial agent
Technical field
The present invention relates to a kind of preparation method of novel inorganic antibacterial agent, belong to the inorganic antiseptic preparing technical field.
Background technology
Human disease-resistant health care be unable to do without antibacterial agent, and antibacterial agent can be divided into organic antibacterial agent and inorganic antiseptic by its composition.Organic antibacterial agent is traditional antibacterial agent, be used widely at present, but their ubiquities volatile, easy decomposition, poor heat resistance and bacterium easily gives birth to defectives such as pesticide resistance.
Because inorganic antiseptic has non-volatile, good heat resistance, be difficult for developing immunity to drugs and advantage such as safety height, become one of current antibacterial agent hot of research and development.Inorganic antiseptic is generally pressed powder, mainly prepares all kinds of antibacterial functions goods in the mode of additive by combining with the application main material.
In the inorganic antibacterial composition, because silver ion has stronger broad-spectrum antiseptic characteristic, therefore, the preparation method that silver ion is combined with inorganic carrier becomes an important directions of current inorganic antiseptic research.But also there are some problems in silver-series antibacterial agent, and the silver ion in this class material is easy grizzle or brown under solar radiation or after being heated to uniform temperature, influences the goods color; In addition, its anti-mycotic efficiency is relatively poor.These have all hindered the application of silver-series antibacterial agent to a certain extent.Superfine Ti O 2Have than intensive ultraviolet absorption and screening ability, higher surface catalysis activity and broad-spectrum sterilization function etc., wherein sterilizing function enjoys people's attention, and it has antibiotic and mildew-proof function simultaneously.But, superfine Ti O 2The bactericidal action that must could rise by illumination (mainly being ultraviolet light) has so just limited its range of application.
Experiment shows: along with reducing of antibacterial agent particle diameter, antibiotic rate progressively increases.This is that the antibiotic powder particles number of Unit Weight increases because particle diameter reduces, thereby has increased the contact area with bacterium, has improved antibacterial effect.So when being index with the antibiotic rate, except the high spot reviews material proportion influences it, granularity also is a factor must considering in the inorganic antiseptic preparation process.
The most of employing of inorganic antiseptic in the market silver ion is main antimicrobial component, natural or synthetic material such as silicate, zeolite etc. are prepared from by operations such as absorption, ion exchanges as carrier, its granularity is thicker, there is antibacterial components set instability in carrier, shortcoming such as easy to change can not satisfy requirement of actual application well.
Summary of the invention
The object of the present invention is to provide ultra-fine level, rerum natura is stable and have the preparation method of the compound inorganic antiseptic of a kind of multicomponent of strong broad-spectrum sterilization effect.
For achieving the above object, as the sedimentation nucleus, metallic compounds such as outer wrapping titanium precipitate with the silver ion sediment in the present invention, and the calcium phosphate precipitation thing wraps up as the second layer, and Separation of Solid and Liquid is after thermal treatment promptly gets the composite antibiosis powder, and its particle diameter is even and reach ultra-fine grade.
A kind of preparation method of superfine composite inorganic antimicrobial agent, its preparation process in turn includes the following steps:
A, be to add AgNO in 1～3 titanium liquid and the muriatic mixed solution to the pH value 3Solution, stirring reaction 0.5～1h;
B, add urea then, at 50～130 ℃ of reaction 1～4h;
C, dropping soluble phosphate, reaction 0.5～1h;
D, the composite surface modifier of adding, reaction 0.3～1h;
E, Separation of Solid and Liquid, the drying that dewaters gets product at 700～1100 ℃ of calcining 2～10h;
Above-mentioned preparation method's molar ratio of material is Ti 4+: Ag +: PO 4 3-=5～15: 0.5～1: 2～10; Ag +: Cl -=1: 1.2～10; Ti 4+: CO (NH 2) 2=1: 2～8.
Above-mentioned titanium liquid is meant the solution of solubility titanium salt, as Ti (SO 4) 2, TiOSO 4, TiCl 4Deng the aqueous solution.
Chloride is meant MCl, M=Na, K, H or NH 4
Or MCl 2, M=Zn, Sn or Cu;
Or MCl 4, one of M=Sn or Zr are any or its mixture.
The main combination with silver ion of the adding of chloride MCl forms AgCl sedimentation nucleus, obviously, if need fully with Ag +Sedimentation forms product nuclear, Cl -The adding mole at least should with Ag +Quite; Simultaneously, muriatic adding also is absolutely necessary, if no chloride exists, the hydrolysis of urea of Jia Ruing discharges ammonia subsequently, will make Ag +Form Ag (OH) 2Precipitation, and then be transformed into Ag 2The O precipitation, Ag 2The appearance of O is unfavorable for secondary parcel subsequently, and the product that finally obtains is not ultra-fine level, and product also exists sees the allochroic problem of light.Chloride MCl 2Or MCl 4Adding purpose one provide Cl -, two provide metal ion among Zn, Sn, Cu, Sn or the Zr, to increase The comprehensive performance.So, Ag +: Cl -Mol ratio be controlled at 1: 1.2～10 better.
In the above-mentioned preparation process, urea is as the sedimentation agent of metal ion, be because in the hydrolysis of urea process along with the continuous generation of ammonia, OH in the solution -Concentration increases gradually, forms the homogeneous precipitation integument in whole solution.Reaction temperature is unsuitable too high, otherwise the isomerization condensation can take place urea, so reaction temperature should not be higher than 130 ℃; In order to guarantee that metal ion can precipitate fully, suitable amount of urea is 1～4 times of its theoretical consumption; Consider that reactant liquor should have higher concentration, urea can solid-state mode add.
Soluble phosphate is meant M 2HPO 4Or MH 2PO 4, M=K or Na consider effect and price factor, select Na for use 2HPO 4Better.
Composite surface modifier is meant the compound system of the surfactant of nonionic and anionic, and nonionic surface active agent can be one or more in AEO-9,6501, OP-10, TX-10, Tween-85, Tween-65, Span-80, the polyethylene glycol-2000; Anionic surfactant can be one or more in AES, LAS, FAS-12, SDS, dispersing agent NNO, Nekal BX-78, the Sodium Polyacrylate.The present invention directly joins composite surface modifier in the reaction system solia particle is carried out surface modification, can prevent the reunion of a primary partical.The surfactant weight ratio of nonionic and anionic is 1: 0.2～2.0.The suitable consumption of composite surface modifier is 0.05～0.4 times of solid dry powder weight.
Because trivalent silver has the sterilizing ability stronger than monovalence silver, therefore, the above-mentioned product that obtains further oxidation processes in potassium peroxydisulfate or sodium peroxydisulfate solution is obtained trivalent silver superfine composite inorganic antimicrobial agent, 30～85 ℃ of reaction temperatures, handled 3～8 hours, and can further improve the antibacterial effect of antibacterial agent.
Certain density titanium liquid is to be prepared through operations such as acidolysis, leaching and isolation of purified by the technical grade metatitanic acid, and acidolysis is excessive slightly with sulfuric acid, to improve the acidolysis yield; The leaching water yield is moderate, and very few leaching is incomplete, excessive then titanium liquid poor stability; Leaching temperature is also moderate, crosses low influence leaching speed and leaching degree, and too high meeting sharply descends titanium liquid stability, and colloid thing content is increased, and premature hydrolysis takes place.
Separation of Solid and Liquid, the drying that dewaters are selected one of following two kinds of methods for use:
A) centrifugation liquid-solid system embathes with organic alcohol after filter cake is fully washed again, 60～110 ℃ of drying 2～8h;
B) centrifugation liquid-solid system, after filter cake is fully washed, azeotropic distillation dehydration in n-butanol.
The present invention compared with prior art has following advantage:
(1) as the sedimentation nucleus, metallic compounds such as outer wrapping titanium precipitate and the calcium phosphate precipitation thing composite inorganic antimicrobial agent of the present invention with the silver ion sediment, and it brings into play the long acting antibiotic effect by the slowly-releasing antibacterial components.Its particle diameter is even, reaches ultra-fine level, has strong bactericidal effect; Because the effect of parcel, antimicrobial component are stable in the salt of phosphoric acid crystalline solid, overcome existing silver-series antibacterial agent to the fungi killing effect not good, easy to change and titanium series antibacterial agent light requirement according to shortcomings such as competence exertion biocidal efficacies.
(2) silver and metallic compounds such as titanium, zirconium, tin and zinc all are antimicrobial component, with phosphate and antimicrobial component compound back drying and high temperature treatment, promptly make salt of phosphoric acid crystalline solid antibacterial agent.This class double salt has the good layered crystal structure of Nasicon type crystal structure or ion-exchange performance, stronger ion-exchange capacity is arranged, and it is by the slowly-releasing antimicrobial component or produce active oxygen and have the durable antibiotic effect.
(3) ultra-fine inorganic antibacterial agent of the present invention can be widely used in textile, plastics, coating, ward off fields such as processing such as pottery and water treatment as additive; Its production cost is low, has good market prospects.
Embodiment
Embodiment 1:
In metatitanic acid: the ratio of 98% sulfuric acid (wt)=1: 2.0～3.0 takes by weighing material respectively, earlier 98% sulfuric acid is diluted to 70～90% with deionized water and is placed in the reactor, with the metatitanic acid porphyrize, sieves through 325～400 mesh sieve, adds in the sulfuric acid again; Start agitator, carry out acidolysis reaction.Reaction temperature is controlled between 70～130 ℃, and the reaction time is controlled at 10～40min; By metatitanic acid: the proportional quantities of deionized water (wt)=1: 3～5 is removed ionized water, adds in the reactor to leach acid hydrolysate, and temperature is controlled between 40～70 ℃; Obtain titanium liquid after leaching insoluble matter, 80～210g/L is (with TiO for its concentration 2Meter, down together), demarcate standby.
The titanium liquid 80ml (concentration is 180g/L) of measuring preparation as stated above is added in the reactor, adds the anhydrous SnCl of 4.52g again 4Be total to 20ml with the 0.50g sodium chloride solution, start agitator, drip 10mlAgNO 3Solution (contains AgNO 31.60g); Add 35.22g urea (adding in solid-state mode, down together) then, reaction 2h; Drip the Na of 80ml again 2HPO 4Solution (contains 20.17g Na 2HPO 412H 2O), stir 1h; In reaction system, add composite surface modification (be made up of AEO-9 and Sodium Polyacrylate, the ratio of both weight is 1: 0.8) 2g, reaction 0.5h.After reaction finished, the centrifugation solid-liquid obtained filter cake, fully washes filter cake, embathes 110 ℃ of dry 2h 2 times with the absolute ethyl alcohol of filter cake with volume again.Dried material is broken up the back in 800 ℃ of calcining 5h, promptly obtain product, record its average grain diameter 50nm.
The antibacterial effect experiment, with reference to " Ministry of Health of the People's Republic of China's disinfection technology standard (2002) " regulation, experimental procedure is as follows:
1, accurately takes by weighing a certain amount of antibacterial agent in liquid nutrient medium, be mixed with predetermined concentration suspension, place conical flask, with 120 ℃ saturated vapor sterilization 25min.
2, ready bacterial classification is added among the aseptic PBS, bacterial concentration is controlled at 105～106cfu/ml.
3, conical flask is fixed on the vibration shaking table, 37 ℃ of constant temperature vibrate with 200r/min speed, and the contact sterilization begins.
4, oscillate to certain hour after, from conical flask, take out sample liquid, by doubly dilution, be inoculated in the plate with the agar tilt-pour process, be inverted in 37 ℃ of incubators and cultivate 24～48h, adopt colony counting method to determine bacterial content in the sample liquid.Carrying out blank assay synchronously opposes in the same old way.
5, the antimicrobial efficiency of antibacterial agent is calculated: and sterilizing rate=1-(clump count of antibiotic sample/in the same old way clump count).
Experimental result shows, concentration 100mg/L, and when unglazed the photograph, the antibacterial agent for preparing according to embodiment 1 reaches 98.5%, 40min killing rate 100% to three kinds of bacterium 30min killing rates such as staphylococcus aureus, Escherichia coli and Candida albicanss.
This antimicrobial powder exposes the 72h nondiscolouring in sunlight, air.
Embodiment 2:
Get the antibacterial agent 1g of embodiment 1 preparation, be added in the potassium persulfate solution of 100ml 0.05M, filter, wash, dry the antibacterial agent that obtains containing trivalent silver then at 50 ℃ of reaction 6h.
Antibacterial experiment is the result show, concentration 100mg/L, and when unglazed the photograph, the antibacterial agent for preparing by embodiment 2 reaches 100% to example 1 described three kinds of bacterium 20min killing rates.
Embodiment 3:
Measure titanium liquid 55ml (concentration is 150g/L), take by weighing ZrOCl by the preparation of example 1 method 28H 2O7.55g is dissolved in the 20ml deionized water, joins in the reactor, starts agitator, drips 10ml AgNO 3Solution (contains AgNO 31.00g); Add 47.07g urea then, reaction 3h; Drip the Na of 80ml at last 2HPO 4Solution (contain Na 2HPO 412H 2O 23.60g), reaction 0.5h, adding composite surface modifier (is made up of OP-10 and Nekal BX-78, the ratio of both weight is 1: 0.4) 1.5g, reaction 1h, after reaction finishes, centrifugation, after fully washing, filter cake embathes 80 ℃ of dry 10h 3 times with 95% ethanol of filter cake again with volume.Dried material through break up, 1000 ℃ the calcining 3h promptly obtain product, its average grain diameter 90nm.
Antibacterial experiment is the result show, as concentration 100mg/L, when unglazed the photograph, example 1 described three kinds of bacterium 30min killing rates reached 100%.
This antimicrobial powder exposes the 72h nondiscolouring in sunlight, air.
Embodiment 4:
Measure titanium liquid 200ml (concentration is 80g/L), take by weighing ZrOCl by the preparation of example 1 method 28H 2O3.80g, anhydrous SnCl 42.68g, AgNO 31.50g, be dissolved in 50,10 respectively, the 20ml deionized water, with ZrOCl 2And SnCl 4Solution joins in the reactor, starts agitator, drips AgNO 3Solution; Add 47.88g urea then, reaction 4h; Drip 120ml Na at last 2HPO 4Solution (contains 23.60gNa 2HPO 412H 2O), reaction 0.5h adds composite surface modifier (be made up of polyethylene glycol-2000 and FAS-12, the ratio of both weight is 1: 1) 1.8g, reaction 1h.After reaction finished, centrifugation was after filter cake is fully washed, drop into azeotropic distillation dehydration (n-butanol addition: water content in the filter cake=2: 3 in the n-butanol, weight ratio), through 120 ℃ of dried materials through break up, 1000 ℃ the calcining 3h promptly obtain product, its average grain diameter 180nm.
Antibacterial experiment is the result show, concentration 100mg/L when unglazed the photograph, reaches 100% to example 1 described three kinds of bacterium 30min killing rates.
This antimicrobial powder exposes the 72h nondiscolouring in sunlight, air.

Claims (9)

1, a kind of preparation method of superfine composite inorganic antimicrobial agent, its preparation process in turn includes the following steps:
A, be to add AgNO in 1～3 titanium liquid and the muriatic mixed solution to the pH value 3Solution, stirring reaction 0.5～1h;
B, add urea then, at 50～130 ℃ of reaction 1～4h;
C, dropping soluble phosphate, reaction 0.5～1h;
D, the composite surface modifier of adding, reaction 0.3～1h;
E, Separation of Solid and Liquid, the drying that dewaters gets product at 700～1100 ℃ of calcining 2～10h;
Above-mentioned preparation method's molar ratio of material is Ti 4+: Ag +: PO 4 3-=5～15: 0.5～1: 2～10; Ag +: Cl -=1: 1.2～10; Ti 4+: CO (NH 2) 2=1: 2～8, the consumption of composite surface modifier is 0.05～0.4 times of solid dry powder weight.
2, the preparation method of superfine composite inorganic antimicrobial agent according to claim 1 is characterized in that: the monovalence silver products that obtains further oxidation processes in persulfate solution can obtain trivalent silver superfine composite inorganic antimicrobial agent.
3, the preparation method of superfine composite inorganic antimicrobial agent according to claim 2 is characterized in that: persulfate is M 2S 2O 8, M=NH wherein 4, Na or K.
4, the preparation method of superfine composite inorganic antimicrobial agent according to claim 1 is characterized in that: titanium liquid is the solution of solubility titanium salt, as Ti (SO 4) 2, TiOSO 4, TiCl 4Solution etc.
5, the preparation method of superfine composite inorganic antimicrobial agent according to claim 1 is characterized in that: titanium liquid obtains by the metatitanic acid sulfuric acid solution.
6, the preparation method of superfine composite inorganic antimicrobial agent according to claim 1 and 2, it is characterized in that: chloride is meant MCl, M=Na, K, H or NH 4
Or MCl 2, M=Zn, Sn or Cu;
Or MCl 4, M=Sn or Zr, one of any or its mixture.
7, the preparation method of superfine composite inorganic antimicrobial agent according to claim 1, it is characterized in that: composite surface modifier is meant the compound system of the surfactant of nonionic and anionic, and nonionic surface active agent can be one or more in AEO-9,6501, OP-10, TX-10, Tween-85, Tween-65, Span-80, the polyethylene glycol-2000; Anionic surfactant can be one or more in AES, LAS, FAS-12, SDS, dispersing agent NNO, Nekal BX-78, the Sodium Polyacrylate, and the surfactant weight ratio of nonionic and anionic is 1: 0.2～2.0.
8, the preparation method of superfine composite inorganic antimicrobial agent according to claim 1 and 2, it is characterized in that: soluble phosphate is meant M 2HPO 4Or MH 2PO 4, M=K or Na.
9, the preparation method of superfine composite inorganic antimicrobial agent according to claim 8 is characterized in that: soluble phosphate is Na 2HPO 4
CNB2005100416268A 2005-01-14 2005-01-14 Method for preparing superfine composite inorganic antimicrobial agent Expired - Fee Related CN1310589C (en)

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CN100341411C (en) * 2006-01-13 2007-10-10 暨南大学 Inorganic compound antibacterial agent, and its preparing method and use
CN100393936C (en) * 2005-08-24 2008-06-11 西北大学 Antibacterial fabric finishing agent and its preparation method
CN101940221A (en) * 2010-08-30 2011-01-12 苏州邦安新材料科技有限公司 Novel sterilizing effervescent tablets and preparation process thereof
CN103011276A (en) * 2012-12-13 2013-04-03 上海纳米技术及应用国家工程研究中心有限公司 Method for preparing silver-loaded titanium oxide-zirconium phosphate composite nanometer material
CN103657688A (en) * 2012-09-12 2014-03-26 安徽迪诺环保新材料科技有限公司 Tungsten-added type nanometre titanium dioxide catalyst for flue gas denitrification and preparation method for catalyst
CN104841015A (en) * 2015-05-21 2015-08-19 吉林大学 High-specific-surface-area silver-loaded titanium dioxide composite antibacterial material and preparation method thereof

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CN1123291C (en) * 2000-04-21 2003-10-08 云南大学 High-temp inorganic antibacterial agent
CN100489040C (en) * 2002-04-29 2009-05-20 中国科学院上海硅酸盐研究所 Composite nano antiseptic titania/silica powder and its preparation
CN1259831C (en) * 2003-11-04 2006-06-21 西安康旺抗菌科技股份有限公司 Inorganic antiseptic of phosphate containing high valence Ag and its preparation method

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CN100393936C (en) * 2005-08-24 2008-06-11 西北大学 Antibacterial fabric finishing agent and its preparation method
CN100341411C (en) * 2006-01-13 2007-10-10 暨南大学 Inorganic compound antibacterial agent, and its preparing method and use
CN101940221A (en) * 2010-08-30 2011-01-12 苏州邦安新材料科技有限公司 Novel sterilizing effervescent tablets and preparation process thereof
CN101940221B (en) * 2010-08-30 2014-02-26 苏州泰利三佳纳米科技有限公司 Novel sterilizing effervescent tablets and preparation process thereof
CN103657688A (en) * 2012-09-12 2014-03-26 安徽迪诺环保新材料科技有限公司 Tungsten-added type nanometre titanium dioxide catalyst for flue gas denitrification and preparation method for catalyst
CN103657688B (en) * 2012-09-12 2015-09-23 安徽迪诺环保新材料科技有限公司 A kind ofly add tungsten type nanometer titanium dioxide Catalysts and its preparation method for denitrating flue gas
CN103011276A (en) * 2012-12-13 2013-04-03 上海纳米技术及应用国家工程研究中心有限公司 Method for preparing silver-loaded titanium oxide-zirconium phosphate composite nanometer material
CN103011276B (en) * 2012-12-13 2015-02-18 上海纳米技术及应用国家工程研究中心有限公司 Method for preparing silver-loaded titanium oxide-zirconium phosphate composite nanometer material
CN104841015A (en) * 2015-05-21 2015-08-19 吉林大学 High-specific-surface-area silver-loaded titanium dioxide composite antibacterial material and preparation method thereof
CN104841015B (en) * 2015-05-21 2017-04-12 吉林大学 High-specific-surface-area silver-loaded titanium dioxide composite antibacterial material and preparation method thereof

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