CN104186545A - Novel large-scale simple preparation method of zeolite zinc-loaded inorganic antibacterial agent - Google Patents
Novel large-scale simple preparation method of zeolite zinc-loaded inorganic antibacterial agent Download PDFInfo
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Abstract
The invention relates to a novel large-scale simple preparation method of a zeolite zinc-loaded inorganic antibacterial agent. According to the method, high-concentration loading of zinc ions in a porous zeolite channel is finished in the ball milling process by utilizing planetary high-energy ball milling equipment, and the zinc content can be 9.0-18.0 percent according to a weight ratio. The high-energy ball milling process integrates powder particle grinding and metal ion exchange, so that the prepared zeolite zinc-loaded inorganic antibacterial agent particles are small in size, uniform in distribution and less prone to aggregation. The preparation method of the zeolite zinc-loaded inorganic antibacterial agent is simple in process, low in production cost and suitable for large-scale batch production, and raw materials are readily available. The zeolite zinc-loaded inorganic antibacterial agent prepared by the invention is good in antibacterial performance and safe to use, does not change color and can be widely applied to antibacterial functional treatment of products such as plastic, rubber, textiles and building materials.
Description
Technical field
The present invention relates to a kind of zeolite and carry zinc inorganic antiseptic.More specifically, the present invention relates to a kind of novel large-scale zeolite and carry the simple method for preparing of zinc inorganic antiseptic.
Background technology
On Vehicles Collected from Market, be applied to superfine powder inorganic antiseptic in the materials such as plastics, weaving, building materials and be generally the carrier compounds such as the zeolite, phosphate, soluble glass, hydroxyapatite of the metal ions such as load silver, copper, zinc, metal ion antimicrobial component, because its carrier is mesoporous or interlaminar action has slow release effect, shows excellent antimicrobial long-acting so be applied in the materials such as plastics, weaving, building materials.Wherein Zeolite support antibacterial agent is an important branch of inorganic antiseptic, utilize the multi-pore channel absorption of zeolitic material itself and exchange interaction by successful metal ion antimicrobial component load, preparation technology is relatively simple, native land is inside and outside very many about preparation, the application study of Zeolite support inorganic antiseptic, and main conditions are listed below:
The development of Zeolite support antibacterial agent starts from day this product river fuel corporation in 1984 and successfully develops first Ag Loaded Zeolite Antimicrobial, commodity are called Zeomic, after the said firm pushes its commercialization to society, people utilize this Ag Loaded Zeolite Antimicrobial to be made into antibacterial socks due to good deodorization effect, antibacterial and safety, so obtain a wide range of applications in Japan and other countries.
Chinese patent CN 1086270C discloses a kind of bactericidal composition and preparation method thereof: synthesized a kind of plastic antimicrobial agent taking silver nitrate, zinc nitrate, zinc sulphate, zinc oxide, dispersant and zeolite as raw material by controlling ratio and certain step between component; this production technology is relatively simple; but the product particle obtaining is larger; only be less than 30 μ m left and right; add in goods and can exert an influence to outward appearance; range of application is limited; and the high-temperature shaping to silver components not in its technique; without special auxiliary agent protection, in use, silver ion is easy to variable color.
Chinese patent CN1283154C discloses a kind of stilbite carrier zine series antibacterial agent: this antibacterial agent is counted 5-8% by weight containing zinc ion content, cost compare is low, antibacterial action is strong, lasting effect is good, but preparation technology's more complicated, the particle that relates to carrier zeolite grinds, ion exchange, flocculation, liquid-solid separation, Washing of Filter Cake, dry, pulverize, multiple links such as high-temperature roasting, wherein Washing of Filter Cake link can produce waste liquor contamination, the fusing point of zeolite is generally 800 DEG C, technique of the present invention is taked 800-100 DEG C of high-temperature roasting 1-2.5h, the cooling part zeolitic material that certainly has is formed bulk again, still need after will pulverizing and could use.
Chinese patent CN101176468A has announced a kind of inorganic complex antimicrobials containing zincium-rare earth and its preparation method and application: this antibacterial agent is taking natural or synthetic ion exchange material as carrier, by liquid phase or solid state ion exchange method zinc supported ion and rare earth ion double activity center, zinc ion content is 6-8wt%, and the content of rare earth ion is 2-4wt%.Antibacterial antiplaque agent spectrum of the present invention is wide, efficiency is high, heat-resisting, discoloration-resistant is good, cost is low; the desirable replacer of carrying silver antimicrobials; but the solid state ion exchange in production technology is only undertaken by simple solid-state grinding; ion exchange condition is insufficient; zinc supported ion concentration is lower, and can cause system antibacterial components distribution portion even, unstable; rare earth compound is often understood the existence of association nuclear radiation element in addition, and made antibacterial agent may have potential radiation hazradial bundle.
Chinese patent CN101884338B has announced a kind of antibacterial agent that contains three kinds of ions of Ag-Cu-Zn: this antibacterial agent is taking epidesmine as carrier; form through the modification of sodium type, the PROCESS FOR TREATMENT such as antibacterial modified, dry; it is very simple that technique seems; but silver contains silver ion; technical process lacks high-temperature shaping link; protect without special auxiliary agent; antibacterial agent in using, be easy to cause silver ion separate out too fast too much and variable color; and the copper ion containing often can be with color, and this system antibacterial agent scope of application is limited.
Chinese patent CN102461561A has announced the preparation method of a kind of zeolite-loaded silver and antibacterial agent thereof: this system antibacterial agent contains 95% zeolite and 5% silver nitrate; composition is simple; antibacterial efficiency is high; but very high silver content can cause cost very high; and process treatment process is without high-temperature shaping processing; without special auxiliary agent protection, therefore discoloration problem can be more serious.Comprehensive literature report is known: the research of current Zeolite support antibacterial agent is very active; the antimicrobial component of load can be silver ion, zinc ion, copper ion and rare earth ion etc.; wherein silver-ion antibiotic activity is the highest; so most widely used general; but material cost is also the highest; and its property easy to change; structure control and technology controlling and process more complicated; and copper ion is because of the color of itself; limit its range of application; the zinc ion that relatively gets up is that combination property is best, and antimicrobial efficiency is on the low side, but can make up by improving adding proportion.In the preparation, ion-exchange process control ratio is stricter for zeolites antibacterial agent in addition, if metal water solution concentration is excessive, can stops up zeolite cavity at surface area silver particle, thereby affect anti-microbial property and the apparent property of zeolite.And if metal water solution concentration is too low, cause zeolite-loaded amount of metal ion on the low side, make antibacterial antiplaque agent activity on the low side, so in a series of zeolite antibacterial agent preparations, ion exchange link is all key control technology.The present invention prepares to use high-energy-milling to integrate powder and grinds and ion load, and the preparation that the relatively simple technique of use completes zeolite carries zinc antibacterial agent, there is not yet Research Literature report.
At present, on market, need all the time a kind ofly to use zeolite safe, constant product quality to carry zinc inorganic antiseptic, more need a kind of simple to operate, cost is lower, the zeolite of high antibacterial activity carries zinc inorganic antiseptic large-scale producing method.For this reason, the inventor has completed the present invention finally through lot of experiments.
Summary of the invention
the technical problem solving
The object of this invention is to provide the novel large-scale simple method for preparing that a kind of zeolite carries zinc inorganic antiseptic.
technical scheme
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of zeolite carries the novel large-scale simple method for preparing of zinc inorganic antiseptic.The method step is as follows:
Steps A slurries preparation: 200-300 weight parts water is added in agitator tank, then add while stirring 90-120 weight portion zeolite, after adding, zeolite continues to add while stirring 50-100 part soluble zinc salt, and stir 30-50min at temperature 90-100 DEG C, described zinc salt is dissolved completely, obtain a kind of mixed serum, for subsequent use;
Step B defibrination: add in high energy ball mill together with the grinding aid of the slurries that steps A is obtained and 0.5-1.0 weight portion, open wet method defibrination program, ball milling 2-3h;
Step C spraying is dry: the slurries that step B has been ground add spray drying treatment in high-speed centrifugal spray dryer, can form the pelletized product of 20 ~ 500 μ m within the 5-30s time, collects dry powder;
Step D pulverizes: the dry powder of step C gained is pulverized through airflow milling to can to obtain product cut size be that the zeolite of 0.5 ~ 10 μ m carries zinc inorganic antiseptic finished product, packed.
A preferred embodiment of the invention, described water is deionized water or distilled water.
According to another kind of preferred embodiment of the present invention, described zeolite is natural zeolite or artificial zeolite, and its grain fineness is greater than 100 orders, and whiteness is greater than 80.
According to another kind of preferred embodiment of the present invention, described soluble zinc salt is at least one in zinc nitrate hexahydrate, Zinc vitriol, zinc chloride or zinc acetate.
According to another kind of preferred embodiment of the present invention, described grinding aid is at least one in triethanolamine, sodium phosphate trimer, polymerized polyalcohol or polycarboxylate.
According to another kind of preferred embodiment of the present invention, described steps A agitator tank material used is the one in stainless steel, enamel or pottery.
According to another kind of preferred embodiment of the present invention, described step B high energy ball mill used is planetary high-energy ball mill.
According to another kind of preferred embodiment of the present invention, the ball-milling technology of described step B is: ball grinder and abrading-ball are stainless steel or zirconia material; Ball radius is approximately large, medium and small three kinds of 8mm, 5.5mm and 3.9mm, and the large, medium and small proportioning of abrading-ball is 1:6:3 or 1:1:1; Material ball ratio is 2:1 or 3:1; Revolution speed is 100-300r/min, autobiography speed 200-600r/min; Ball milling 2-3h.
Preferably, the another kind of preferred embodiment that this is bright, the ball-milling technology of described step B is: ball grinder and abrading-ball are zirconia material; Ball radius is approximately large, medium and small three kinds of 8mm, 5.5mm and 3.9mm, and the large, medium and small proportioning of abrading-ball is 1:6:3; Material ball ratio is 2:1; Revolution speed is 250r/min, autobiography speed 500r/min; Ball milling 2.5h.
The principle of institute of the present invention foundation is: in recent years, mechanical force and chemical is as an emerging cross discipline, day by day be subject to the attention of countries in the world, and in ball milling, utilize the principle of mechanical force and chemical to prepare various powder body materials and become a focus of current powder field of scientific study, in Process During High Energy Ball Milling, powder particle is in higher-energy state, the moment bumping at ball and powder particle produces high temperature, High Pressure, form high-activity area, can bring out moment physics herein, chemical reaction, directly increase spontaneous incorgruous diffusion rate, also can improve reaction temperature.The present invention is on planetary high-energy ball mill, slurries to zeolite and soluble zinc salt stirring formation carry out ball milling by certain technique, according to mechanical force and chemical principle, make zeolite granular and zinc ion in upper state, increase spontaneous incorgruous diffusion rate, bring out both sides' physics, chemical action.That is to say that high energy wet ball grinding technique of the present invention has reduced zeolite powder particle size on the one hand, has increased specific surface area; More crucial is to impel zinc ion easily to penetrate in zeolite loose structure on the other hand, carries out ion exchange, completes active component load.Integrating powder granule and pulverize and the high-energy ball-milling process of ion exchange, is key control technology prepared by inorganic antiseptic of the present invention, and current zeolite carries Research Literature prepared by zinc antibacterial agent not yet report.
The present invention will be described below in more detail.
The present invention relates to a kind of simple method for preparing of the novel large-scale Nano Silver hydrosol.The method step is as follows:
Steps A slurries preparation: 200-300 weight parts water is added in agitator tank, then add while stirring 90-120 weight portion zeolite, after adding, zeolite continues to add while stirring 50-100 part soluble zinc salt, and stir 30-50min at temperature 90-100 DEG C, described zinc salt is dissolved completely, obtain a kind of mixed serum, for subsequent use.
A preferred embodiment of the invention, described water is deionized water or distilled water.
According to another kind of preferred embodiment of the present invention, described zeolite is natural zeolite or artificial zeolite, and its grain fineness is greater than 100 orders, and whiteness is greater than 80.
Natural zeolite is the hydrous alumino silicates mineral of the metal ions such as Na, Ca.Zeolite type is various, and up to the present, natural zeolite more than 40 kinds have been found in the whole world.China's zeolite rich in mineral resources, within 1972, find first zeolite deposit at Jinyun county, Zhejiang province, at present the whole nation has found that the zeolite place of production more than 400 locates, the zeolite kind that China has found has clinoptilolite, modenite, seebachite, chabasie, phillipsite, analcime, yugawaralite, wairakite, heulandite, laumontite, foresite, sodalite, wherein maximum with the exploitation of clinoptilolite, modenite, chabasie, heulandite.Zeolite chemical composition is very complicated, kind difference, and composition has very big-difference.The structural formula of zeolite can be expressed as Ax/q[(AlO2) x.(Si02) y] nH20, wherein A is the cations such as Ca, Na, K, Ba, Sr, and q is cation electricity price, and n is water molecule number, and x is Al atomicity, and y is Si atomicity, and y and x ratio are conventionally between l～5, and x+y is tetrahedral number in unit cell.Zeolite also has good ion-exchange performance, and the movably cation that distributing in a large number in the hole of zeolite crystal can exchange with other cations, as clinoptilolite and modenite etc. all have very high cation exchange capacity.This structural property of zeolite makes it have excellent absorption, ion exchange and catalytic performance etc., thereby is widely used in construction material, environment-friendly materials, light industry, farming and animal husbandry etc., has important environment, society and economic benefit.The present invention's natural zeolite used is the one in clinoptilolite, modenite, foresite or heulandite etc., belongs to commercially available prod.
Artificial zeolite, also be synthetic zeolite, it is artificial synthetic inorganic ion exchanger, by the product with irregular structure making after the mixing such as sodium carbonate, caustic potash, feldspar, kaolinite melting, its function is similar to natural zeolite, and absorption property is stronger than natural zeolite, ion-exchange performance is also better, current water processing filter medium, cultivate water modifying agent, coating and adhesive additive, the detergent additive etc. of being mainly used in.The present invention's artificial zeolite used is A type zeolite or ZSM type zeolite, belongs to commercially available prod.
Preferably, zeolite of the present invention is natural zeolite, with low cost.
According to another kind of preferred embodiment of the present invention, described soluble zinc salt is at least one in zinc nitrate hexahydrate, Zinc vitriol, zinc chloride or zinc acetate.
Zinc nitrate hexahydrate, CAS is numbered 10196-18-6, and chemical formula is Zn (NO
3)
26 (H
2o), molecular weight is 297.48, soluble in water.The present invention's zinc nitrate hexahydrate used is the above product of technical grade, commercially available.
Zinc vitriol, CAS is numbered 7446-20-0, and chemical formula is Zn (SO
4)
27 (H
2o), molecular weight is 287.56, soluble in water.The present invention's Zinc vitriol used is the above product of technical grade, commercially available.
Zinc chloride, CAS is numbered 231-592-0, and chemical formula is ZnCl
2, molecular weight is 136.3, soluble in water.The present invention's zinc chloride used is the above product of technical grade, commercially available.
Zinc acetate, also claims zinc acetate, and CAS is numbered 557-34-6, and chemical formula is Zn (CH
3cOO)
2, molecular weight is 183.48, soluble in water.The present invention's zinc acetate used is the above product of technical grade, commercially available.
Preferably, the present invention's soluble zinc salt used is zinc nitrate hexahydrate or Zinc vitriol.
More preferably, the present invention's soluble zinc salt used is Zinc vitriol.
According to another kind of preferred embodiment of the present invention, described grinding aid is at least one in triethanolamine, sodium phosphate trimer, polymerized polyalcohol or polycarboxylate.
Triethanolamine, CAS is numbered 102-71-6, and chemical formula is (HOCH2CH2) 3N, colourless to faint yellow transparent thick liquid, and micro-have an ammonia taste, becomes colourless to faint yellow cubic system crystal when low temperature.While being placed in air, color deepens gradually.Soluble in water, ethanol, acetone, glycerine and ethylene glycol etc., be slightly soluble in benzene, ether and carbon tetrachloride etc., in non-polar solven, dissolves hardly.Flammable, low toxicity, avoids contacting with oxidant, acids.The present invention's triethanolamine used is the above product of technical grade, commercially available.
Sodium phosphate trimer, CAS is numbered 7758-29-4, and molecular formula is Na
5p
3o
10, white powder crystallization, mobility is better, soluble in water, and its aqueous solution is alkalescence, the important auxiliary agent of one in synthetic detergent.The present invention's sodium phosphate trimer used is the above product of technical grade, commercially available.
Polymerized polyalcohol, the liquid mixture of the gas chromatographies such as polyalcohol and polymerized polyalcohol, polyalcohol amine, dark-brown liquid.Main component comprises: diethylene glycol, glycerine, two polyglycerols, three polyglycerols, triethanolamine (TEA), sodium soap and water.This product is nontoxic, corrosion-free, non-inflammable and explosive, meets JC/T667-2004 standard-required.Conventionally polymerized polyalcohol, as the novel material of cement grinding aid, can reduce grinding aid production cost more than 10%.The present invention's polymerized polyalcohol used is the above product of technical grade, commercially available.
Polycarboxylate, its molecule forms " pectination " or " dendroid " structure by " MOLECULE DESIGN " is artificial, and on molecular backbone, is connected to many side chains (side chain) that have certain length and rigidity.The current cement water reducing agent that is mainly used in, on main chain, also have and can make the charged sulfonate of cement granules or other group, can play the effect of traditional water reducer, once the more important thing is that main chain is adsorbed on after cement particle surface, the side chain of side chain and other particle surface forms crossings on different level, hinder particle close to each other, thereby reached dispersion (being diminishing) effect.This sterically hindered effect does not weaken with time lengthening, and therefore, the peptizaiton of polycarboxylate water-reducer is more lasting.The present invention's polycarboxylate used is the above product of technical grade, commercially available.
Preferably, grinding aid of the present invention is sodium phosphate trimer or polymerized polyalcohol.
According to another kind of preferred embodiment of the present invention, described steps A agitator tank material used is the one in stainless steel, enamel or pottery.Agitator tank also can be water tank, can stir material, the processing such as mixture, mediation, homogeneous, is widely used in the industries such as coating, medicine, building materials, chemical industry, pigment, resin, food, scientific research.The present invention's agitator tank used is the enamel material product of Yancheng City Qi Lian power equipment Co., Ltd of Jiangsu Province production and sales.
Step B defibrination: add in high energy ball mill together with the grinding aid of the slurries that steps A is obtained and 0.5-1.0 weight portion, open wet method defibrination program, ball milling 2-3h.
A preferred embodiment of the invention, described step B high energy ball mill used is planetary high-energy ball mill.
Planetary high-energy ball mill be mix, the indispensable device of fine grinding, new product development and batch production new and high technology material.Its operation principle is that several ball mill tanks of making again high speed autobiography with rotating disk revolution are housed on the circumference of rotating disc, and the abrading-ball in ball grinder, under the effect of inertia force, forms very large high-frequency percussion and friction to material, carries out quick fine grinding.The present invention's planetary ball mill used is the vertical type of production planetary ball mill that Changsha Tian Chuan powder technology Co., Ltd produces.
According to another kind of preferred embodiment of the present invention, the ball-milling technology of described step B is: ball grinder and abrading-ball are stainless steel or zirconia material; Ball radius is approximately large, medium and small three kinds of 8mm, 5.5mm and 3.9mm, and the large, medium and small proportioning of abrading-ball is 1:6:3 or 1:1:1; Material ball ratio is 2:1 or 3:1; Revolution speed is 100-300r/min, autobiography speed 200-600r/min; Ball milling 2-3h.Zeolite powder particle size of the present invention, zinc ion load capacity and the load effect on zeolite all has much relations with abrading-ball size proportioning, material ball ratio, machine public affairs (certainly) rotating speed, milling time etc.As low in rotating speed, material and spheroid shock dynamics are inadequate, and fineness of grind is inadequate, extends milling time and also may not necessarily reach ideal effect; Speed is fast, also may cause energy waste, and makes material energy too high, tends to cause sub-micron-powder secondary agglomeration and ion exchange difficulty, and particularly milling time is oversize, affects especially production efficiency, increases energy consumption.
Preferably, the another kind of preferred embodiment that this is bright, the ball-milling technology of described step B is: ball grinder and abrading-ball are zirconia material; Ball radius is approximately large, medium and small three kinds of 8mm, 5.5mm and 3.9mm, and the large, medium and small proportioning of abrading-ball is 1:6:3; Material ball ratio is 2:1; Revolution speed is 250r/min, autobiography speed 500r/min; Ball milling 2.5h.
Step C spraying is dry: the slurries that step B has been ground add spray drying treatment in high-speed centrifugal spray dryer, can form the pelletized product of 20 ~ 500 μ m within the 5-30s time, collects dry powder.
A preferred embodiment of the invention, described step C high-speed centrifugal spray dryer used is a kind of new and effective drying process equipment.It can make solution, emulsion, pasty liquid and heat sensitive material spray-dried.General in seconds transpiring moisture changes the powdery, graininess hollow ball or the circle pelletized product that meet production requirement into, is the desirable drying equipment of the industries such as pharmacy biotechnology, chemical industry.The present invention's spray dryer used is the LPG series of high speed centrifugal spray dryer of Qianjiang Drying Equipment Co., Ltd., Hangzhou's production and sales.
Step D pulverizes: the dry powder of step C gained is pulverized through airflow milling to can to obtain product cut size be that the zeolite of 0.5 ~ 10 μ m carries zinc inorganic antiseptic finished product, packed.
A preferred embodiment of the invention, described airflow milling is Horizontal disc (flat) airflow milling, to spray formula airflow milling or fluid bed to spray formula airflow milling.The present invention's airflow milling used is the AP series of disks formula airflow milling that Weifang Jinghua Powder Engineering Equipment Co.Ltd produces.
According to another kind of preferred embodiment of the present invention, the prepared zeolite obtaining of the present invention carries zinc inorganic antiseptic and has many hollow structures, and the easily moisture absorption, so must seal preservation.
According to another kind of preferred embodiment of the present invention, it is white or canescence superfines that the prepared zeolite obtaining of the present invention carries zinc inorganic antiseptic, grain diameter is 0.5 ~ 10 μ m, and described zeolite carries the content of zinc ion in zinc inorganic antiseptic by weight being 9.0-18%.
According to another kind of preferred embodiment of the present invention, the prepared zeolite obtaining of the present invention carries zinc inorganic antibacterial the minimal inhibitory concentration of Escherichia coli and staphylococcus aureus is respectively and is less than or equal to 312ppm and is less than or equal to 156ppm, and is 0.5-2.0% by weight for the preferred adding proportion of antibacterial functionalized processing of the products such as plastics, rubber, weaving, building materials.
Describe the Performance Detection test that zeolite prepared by the present invention carries zinc inorganic antiseptic below in detail.
Detection method and testing result are as follows.
A, zeolite of the present invention carry the powder granularity test of zinc inorganic antiseptic:
Prepared zeolite is carried to zinc inorganic antiseptic absolute ethyl alcohol and make dispersion medium, on laser particle analyzer, test.Its result of the test is powder D
50< 1.5 μ m, D
90< 2.5 μ m, and maximum particle diameter < 10 μ m.
B, zeolite of the present invention carry the zinc content measuring of zinc inorganic antiseptic:
Carry out zinc content measuring by the prepared inorganic antiseptic of standard GB/T/T 6730.53-2004 " the mensuration flame atomic absorption spectrometry of iron ore zinc content " the present invention.The antibacterial agent zinc ion content obtaining by different ratios of raw materials is by weight being 9.0-18%.
C, zeolite of the present invention carry minimal inhibitory concentration (MIC) test of zinc inorganic antiseptic:
Zeolite of the present invention carries zinc inorganic antiseptic minimal inhibitory concentration to be tested according to Ministry of Public Health's disinfection technology standard (version in 2002) 2.1.7.3, and test bacterial classification is Escherichia coli and staphylococcus aureus, and its result of the test is listed in table 1.
Table 1 zeolite carries minimal inhibitory concentration (MIC) result of the test of zinc inorganic antiseptic
D, zeolite of the present invention carry the antibacterial effect evaluation test that zinc inorganic antiseptic is applied on plastics:
First the zeolite of being prepared by the present invention carries zinc inorganic antiseptic by weight adding in polypropylene (PP) plastic resin through plastics molding process for 0.5-2.0% ratio, making diameter is 100mm, thickness is 0.5mm plastics disks, then the film applicator coating test antibacterial effect specifying by standard QB/T 2591-2003 " antibiotic plastic-anti-microbial property test method and antibacterial effect " standard, and the durable antibacterial effect of the method specifying according to JC/T 939-2004 " antibiotic plastic pipes for building " standard test sample, its testing experiment sample treatment condition for to soak 16h in (50 ± 5) ° C water.Test bacterial classification is Escherichia coli (ATCC25922) and staphylococcus aureus (ATCC6538).Its result of the test is listed in table 2.
Table 2 has added the PP plastic sheet anti-microbial property result of the test that zeolite carries zinc inorganic antiseptic
The above results clearly illustrates that, zeolite prepared by the present invention carries zinc inorganic antiseptic sub-micron-powder maximum particle diameter and is less than 10 μ m, is substantially distributed between 0.5-10 μ m; It is 9.0-18% by weight that zeolite prepared by the present invention carries zinc content in zinc antibacterial agent; Zeolite prepared by the present invention carries zinc inorganic antiseptic and Escherichia coli, staphylococcus aureus minimal inhibitory concentration (MIC) are respectively are less than or equal to 312ppm, are less than or equal to 156ppm, and bacteriostatic activity is remarkable; Added the polypropylene plastics that zeolite prepared by the present invention carries zinc inorganic antiseptic Escherichia coli and staphylococcus aureus antibiotic rate be all greater than to 99.9%, and through its antibiotic rate after soaking 16h in (50 ± 5) ° C hot water and processing still higher than 90%.
beneficial effect]
The present invention has following beneficial effect:
Use conventional equipment, technique is simple, pollution-free, environmentally friendly, is convenient to large-scale industrial production; It is little, safe to use that zeolite prepared by the present invention carries zinc inorganic antiseptic powder granule granularity, anti-microbial property is good, stability is splendid, without discoloration problem, add in plastic products through after soaking 16h in (50 ± 5) ° C hot water and processing to the antibiotic rate of Escherichia coli and staphylococcus aureus still higher than 90%, can be applicable to the antibacterial functionalized processing for products such as plastics, rubber, weaving, building materials, and production cost is low, has the very strong market competitiveness.
[embodiment]
To understand better the present invention by following these embodiment.
embodiment 1:zeolite of the present invention carries the preparation of zinc inorganic antiseptic
Steps A slurries preparation: 200 weight parts waters are added in the agitator tank of Yancheng City Qi Lian power equipment Co., Ltd of Jiangsu Province production, then add while stirring 100 weight portion zeolites, after adding, zeolite continues to add while stirring 70 parts of zinc nitrate hexahydrates, and stir 40min at temperature 90-100 DEG C, described zinc salt is dissolved completely, obtain a kind of mixed serum, for subsequent use;
Step B defibrination: add together with the sodium phosphate trimer of the slurries that steps A is obtained and 0.5 weight portion in the vertical type of production planetary ball mill of Changsha Tian Chuan powder technology Co., Ltd production, open wet method defibrination program, ball milling 2h.Ball milling condition is: ball grinder and abrading-ball are zirconia material; Ball radius is approximately large, medium and small three kinds of 8mm, 5.5mm and 3.9mm, and the large, medium and small proportioning of abrading-ball is 1:1:1; Material ball ratio is 3:1; Revolution speed is 200r/min, autobiography speed 300r/min;
Step C spraying is dry: the slurries that step B has been ground add spray drying treatment in the high-speed centrifugal spray dryer that Qianjiang Drying Equipment Co., Ltd., Hangzhou produces, and within the 10-20s time, can form pelletized product, collect dry powder;
Step D pulverizes: the airflow milling pulverizing that the dry powder of step C gained is produced through Weifang Jinghua Powder Engineering Equipment Co.Ltd can obtain zeolite and carry zinc inorganic antiseptic finished product, packs.
embodiment 2:zeolite of the present invention carries the preparation of zinc inorganic antiseptic
Steps A slurries preparation: 250 weight parts waters are added in the agitator tank of Yancheng City Qi Lian power equipment Co., Ltd of Jiangsu Province production, then add while stirring 120 weight portion zeolites, after adding, zeolite continues to add while stirring 80 parts of Zinc vitriols, and stir 50min at temperature 90-100 DEG C, described zinc salt is dissolved completely, obtain a kind of mixed serum, for subsequent use;
Step B defibrination: add together with the polymerized polyalcohol of the slurries that steps A is obtained and 0.8 weight portion in the vertical type of production planetary ball mill of Changsha Tian Chuan powder technology Co., Ltd production, open wet method defibrination program, ball milling 3h.Ball milling condition is: ball grinder and abrading-ball are zirconia material; Ball radius is approximately large, medium and small three kinds of 8mm, 5.5mm and 3.9mm, and the large, medium and small proportioning of abrading-ball is 1:1:1; Material ball ratio is 3:1; Revolution speed is 300r/min, autobiography speed 500r/min;
Step C spraying is dry: the slurries that step B has been ground add spray drying treatment in the high-speed centrifugal spray dryer that Qianjiang Drying Equipment Co., Ltd., Hangzhou produces, and within the 20-30s time, can form pelletized product, collect dry powder;
Step D pulverizes: the airflow milling pulverizing that the dry powder of step C gained is produced through Weifang Jinghua Powder Engineering Equipment Co.Ltd can obtain zeolite and carry zinc inorganic antiseptic finished product, packs.
embodiment 3:zeolite of the present invention carries the preparation of zinc inorganic antiseptic
Steps A slurries preparation: 200 weight parts waters are added in the agitator tank of Yancheng City Qi Lian power equipment Co., Ltd of Jiangsu Province production, then add while stirring 100 weight portion zeolites, after adding, zeolite continues to add while stirring 60 parts of zinc chloride, and stir 40min at temperature 90-100 DEG C, described zinc salt is dissolved completely, obtain a kind of mixed serum, for subsequent use;
Step B defibrination: add together with the triethanolamine of the slurries that steps A is obtained and 0.5 weight portion in the vertical type of production planetary ball mill of Changsha Tian Chuan powder technology Co., Ltd production, open wet method defibrination program, ball milling 3h.Ball milling condition is: ball grinder and abrading-ball are zirconia material; Ball radius is approximately large, medium and small three kinds of 8mm, 5.5mm and 3.9mm, and the large, medium and small proportioning of abrading-ball is 1:6:3; Material ball ratio is 2:1; Revolution speed is 300r/min, autobiography speed 600r/min;
Step C spraying is dry: the slurries that step B has been ground add spray drying treatment in the high-speed centrifugal spray dryer that Qianjiang Drying Equipment Co., Ltd., Hangzhou produces, and within the 5-20s time, can form pelletized product, collect dry powder;
Step D pulverizes: the airflow milling pulverizing that the dry powder of step C gained is produced through Weifang Jinghua Powder Engineering Equipment Co.Ltd can obtain zeolite and carry zinc inorganic antiseptic finished product, packs.
embodiment 4:zeolite of the present invention carries the preparation of zinc inorganic antiseptic
Steps A slurries preparation: 250 weight parts waters are added in the agitator tank of Yancheng City Qi Lian power equipment Co., Ltd of Jiangsu Province production, then add while stirring 95 weight portion zeolites, after adding, zeolite continues to add while stirring 65 parts of zinc acetates, and stir 50min at temperature 90-100 DEG C, described zinc salt is dissolved completely, obtain a kind of mixed serum, for subsequent use;
Step B defibrination: add together with the polycarboxylate of the slurries that steps A is obtained and 0.5 weight portion in the vertical type of production planetary ball mill of Changsha Tian Chuan powder technology Co., Ltd production, open wet method defibrination program, ball milling 2.5h.Ball milling condition is: ball grinder and abrading-ball are stainless steel; Ball radius is approximately large, medium and small three kinds of 8mm, 5.5mm and 3.9mm, and the large, medium and small proportioning of abrading-ball is 1:1:1; Material ball ratio is 3:1; Revolution speed is 280r/min, autobiography speed 400r/min;
Spray drying treatment in the high-speed centrifugal spray dryer that Qianjiang Drying Equipment Co., Ltd., Hangzhou produces can form pelletized product within the 5-20s time, collects dry powder;
Step D pulverizes: the airflow milling pulverizing that the dry powder of step C gained is produced through Weifang Jinghua Powder Engineering Equipment Co.Ltd can obtain zeolite and carry zinc inorganic antiseptic finished product, packs.
embodiment 5:zeolite of the present invention carries the preparation of zinc inorganic antiseptic
Steps A slurries preparation: 300 weight parts waters are added in the agitator tank of Yancheng City Qi Lian power equipment Co., Ltd of Jiangsu Province production, then add while stirring 90 weight portion zeolites, after adding, zeolite continues to add while stirring 100 parts of Zinc vitriols, and stir 50min at temperature 90-100 DEG C, described zinc salt is dissolved completely, obtain a kind of mixed serum, for subsequent use;
Step B defibrination: add together with the sodium phosphate trimer of the slurries that steps A is obtained and 1.0 weight portions in the vertical type of production planetary ball mill of Changsha Tian Chuan powder technology Co., Ltd production, open wet method defibrination program, ball milling 3h.Ball milling condition is: ball grinder and abrading-ball are zirconia material; Ball radius is approximately large, medium and small three kinds of 8mm, 5.5mm and 3.9mm, and the large, medium and small proportioning of abrading-ball is 1:1:1; Material ball ratio is 3:1; Revolution speed is 300r/min, autobiography speed 600r/min;
Step C spraying is dry: the slurries that step B has been ground add spray drying treatment in the high-speed centrifugal spray dryer that Qianjiang Drying Equipment Co., Ltd., Hangzhou produces, and within the 20-30s time, can form pelletized product, collect dry powder;
Step D pulverizes: the airflow milling pulverizing that the dry powder of step C gained is produced through Weifang Jinghua Powder Engineering Equipment Co.Ltd can obtain zeolite and carry zinc inorganic antiseptic finished product, packs.
Adopt the method for testing of describing in this specification, tested particle size and zinc content that the present embodiment 1-6 prepares zeolite and carry zinc inorganic antiseptic, it the results are shown in table 3 and table 4; Tested the anti-microbial property that the present embodiment 1-6 prepares zeolite and carry zinc inorganic antiseptic, its test result lists in table 5 and table 6.
Table 3: zeolite prepared by embodiment 1-6 carries the particle size result of the test of zinc inorganic antiseptic
Table 4: zeolite prepared by embodiment 1-6 carries the zinc content result of the test of zinc inorganic antiseptic
Table 5: zeolite prepared by embodiment 1-6 carries the MIC result of the test of zinc inorganic antiseptic
Table 6: zeolite prepared by embodiment 1-6 carries zinc inorganic antiseptic to be applied in polypropylene (PP) plastics
Antibacterial tests result (antibacterial agent working concentration is 1.0%)
Claims (10)
1. zeolite carries a novel large-scale simple method for preparing for zinc inorganic antiseptic, it is characterized in that the step of the method is as follows:
Steps A slurries preparation: 200-300 weight parts water is added in agitator tank, then add while stirring 90-120 weight portion zeolite, after adding, zeolite continues to add while stirring 50-100 part soluble zinc salt, and stir 30-50min at temperature 90-100 DEG C, described zinc salt is dissolved completely, obtain a kind of mixed serum, for subsequent use;
Step B defibrination: together with the grinding aid of the slurries that steps A is obtained and 0.5-1.0 weight portion, add in high energy ball mill, open wet method defibrination program, ball milling 2-3h, its ball milling condition is: ball grinder and abrading-ball are stainless steel or zirconia material; Ball radius is approximately large, medium and small three kinds of 8mm, 5.5mm and 3.9mm, and the large, medium and small proportioning of abrading-ball is 1:6:3 or 1:1:1; Material ball ratio is 2:1 or 3:1; Revolution speed is 100-300r/min, autobiography speed 200-600r/min;
Step C spraying is dry: the slurries that step B has been ground add spray drying treatment in high-speed centrifugal spray dryer, can form the pelletized product of 20 ~ 500 μ m within the 5-30s time, collects dry powder;
Step D pulverizes: the dry powder of step C gained is pulverized through airflow milling to can to obtain product cut size be that the zeolite of 0.5 ~ 10 μ m carries zinc inorganic antiseptic finished product, packed.
2. preparation method according to claim 1, is characterized in that described steps A water used is deionized water or distilled water.
3. preparation method according to claim 1, is characterized in that described steps A zeolite used is natural zeolite or artificial zeolite, and its grain fineness is greater than 100 orders, and whiteness is greater than 80.
4. preparation method according to claim 1, is characterized in that described steps A soluble zinc salt used is at least one in zinc nitrate hexahydrate, Zinc vitriol, zinc chloride or zinc acetate.
5. preparation method according to claim 1, is characterized in that described step B grinding aid used is at least one in triethanolamine, sodium phosphate trimer, polymerized polyalcohol or polycarboxylate.
6. preparation method according to claim 1, is characterized in that described steps A agitator tank material used is the one in stainless steel, enamel or pottery.
7. preparation method according to claim 1, is characterized in that described step B high energy ball mill used is planetary high-energy ball mill.
8. preparation method according to claim 1, is characterized in that the ball-milling technology of described step B is: ball grinder and abrading-ball are stainless steel or zirconia material; Ball radius is approximately large, medium and small three kinds of 8mm, 5.5mm and 3.9mm, and the large, medium and small proportioning of abrading-ball is 1:6:3 or 1:1:1; Material ball ratio is 2:1 or 3:1; Revolution speed is 100-300r/min, autobiography speed 200-600r/min; Ball milling 2-3h.
9. the zeolite obtaining according to method described in any one claim in claim 1-8 carries zinc inorganic antiseptic, it is characterized in that it is white or canescence superfines that described zeolite carries zinc inorganic antiseptic, grain diameter is 0.5 ~ 10 μ m, and described zeolite carries the content of zinc ion in zinc inorganic antiseptic by weight being 9.0-18%.
10. the zeolite obtaining according to method described in any one claim in claim 1-8 carries zinc inorganic antiseptic, it is characterized in that described zeolite silver base inorganic antibacterial agent is respectively and is less than or equal to 312ppm and is less than or equal to 156ppm the minimal inhibitory concentration of Escherichia coli and staphylococcus aureus, and be 0.5-2.0% by weight for the preferred adding proportion of antibacterial functionalized processing of the products such as plastics, rubber, weaving, building materials.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105794841A (en) * | 2014-12-26 | 2016-07-27 | 财团法人工业技术研究院 | Antibacterial composite material and manufacturing method thereof |
| CN106269763A (en) * | 2016-08-31 | 2017-01-04 | 孟玲 | Culture dish antibacterial cleaning machine |
| CN108726531A (en) * | 2018-07-02 | 2018-11-02 | 洛阳建龙微纳新材料股份有限公司 | A kind of Zn ion modifications zeolite molecular sieve and its preparation method and application |
| CN111000114A (en) * | 2020-01-08 | 2020-04-14 | 汪博文 | Preparation method of inorganic antibacterial agent for feed |
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| CN112741111A (en) * | 2020-12-31 | 2021-05-04 | 江苏万源新材料股份有限公司 | Antibacterial molecular sieve and preparation method thereof |
| CN113801378A (en) * | 2021-09-23 | 2021-12-17 | 沈阳市津浩科技有限公司 | Ionic liquid-loaded zeolite rubber reinforcing agent and preparation method thereof |
| CN115025823A (en) * | 2022-05-23 | 2022-09-09 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Method for doping metal cations into zeolite |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385072A (en) * | 2002-01-21 | 2002-12-18 | 太原理工大学 | Nano silicate antibiosis composition and process for preparing same |
| CN1483318A (en) * | 2002-09-16 | 2004-03-24 | 北京市建筑材料科学研究院 | Stilbite carrier zine series inorganic germicide |
| CN1531851A (en) * | 2003-03-20 | 2004-09-29 | 蔡惠萍 | Method for preparing inorganic antibiotic primary liquid |
| CN1561745A (en) * | 2004-04-02 | 2005-01-12 | 吉林大学 | Silicate base zincoxide ion nano hole composite material and board spectrum bacteria inhibitor and sterilizer |
| CN1762218A (en) * | 2005-10-26 | 2006-04-26 | 太原理工大学 | Method for inhibiting discoloration of silver-series antibacterial agent |
| CN101176468A (en) * | 2007-11-28 | 2008-05-14 | 暨南大学 | Inorganic complex antimicrobials containing zincium-rare earth as well as preparation method and application thereof |
| CN102939993A (en) * | 2012-11-13 | 2013-02-27 | 浙江大学 | Copper-carrying shell powder antibacterial agent and preparation method thereof |
| CN103691967A (en) * | 2014-01-09 | 2014-04-02 | 李泽国 | Novel large-scale simple preparation method of nano-silver hydrosol |
-
2014
- 2014-08-09 CN CN201410388858.XA patent/CN104186545B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385072A (en) * | 2002-01-21 | 2002-12-18 | 太原理工大学 | Nano silicate antibiosis composition and process for preparing same |
| CN1483318A (en) * | 2002-09-16 | 2004-03-24 | 北京市建筑材料科学研究院 | Stilbite carrier zine series inorganic germicide |
| CN1531851A (en) * | 2003-03-20 | 2004-09-29 | 蔡惠萍 | Method for preparing inorganic antibiotic primary liquid |
| CN1561745A (en) * | 2004-04-02 | 2005-01-12 | 吉林大学 | Silicate base zincoxide ion nano hole composite material and board spectrum bacteria inhibitor and sterilizer |
| CN1762218A (en) * | 2005-10-26 | 2006-04-26 | 太原理工大学 | Method for inhibiting discoloration of silver-series antibacterial agent |
| CN101176468A (en) * | 2007-11-28 | 2008-05-14 | 暨南大学 | Inorganic complex antimicrobials containing zincium-rare earth as well as preparation method and application thereof |
| CN102939993A (en) * | 2012-11-13 | 2013-02-27 | 浙江大学 | Copper-carrying shell powder antibacterial agent and preparation method thereof |
| CN103691967A (en) * | 2014-01-09 | 2014-04-02 | 李泽国 | Novel large-scale simple preparation method of nano-silver hydrosol |
Non-Patent Citations (4)
| Title |
|---|
| SELAMI DEMIRCI等: "Antimicrobial Properties of Zeolite-X and Zeolite-A Ion-Exchanged with Silver, Copper, and Zinc Against a Broad Range of Microorganisms", 《APPL BIOCHEM BIOTECHNOL》 * |
| 倪星元等: "《纳米材料制备技术》", 31 January 2008, 化学工业出版社 * |
| 凌世海: "《固体制剂（第3版）》", 31 March 2003, 化学工业出版社 * |
| 曾晓希等: "载锌沸石抗菌剂的制备及其在PE薄膜中的应用", 《包装工程》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105794841A (en) * | 2014-12-26 | 2016-07-27 | 财团法人工业技术研究院 | Antibacterial composite material and manufacturing method thereof |
| CN105794841B (en) * | 2014-12-26 | 2018-10-16 | 财团法人工业技术研究院 | Antibacterial composite material and manufacturing method thereof |
| CN106269763A (en) * | 2016-08-31 | 2017-01-04 | 孟玲 | Culture dish antibacterial cleaning machine |
| CN108726531A (en) * | 2018-07-02 | 2018-11-02 | 洛阳建龙微纳新材料股份有限公司 | A kind of Zn ion modifications zeolite molecular sieve and its preparation method and application |
| CN111000114A (en) * | 2020-01-08 | 2020-04-14 | 汪博文 | Preparation method of inorganic antibacterial agent for feed |
| CN111233491A (en) * | 2020-03-15 | 2020-06-05 | 雷志刚 | Method for preparing inorganic powder |
| CN111727793A (en) * | 2020-05-22 | 2020-10-02 | 贵州省亚热带作物研究所 | Stereoscopic cultivation method for crude drug tsaoko in karst mountain land |
| CN112741111A (en) * | 2020-12-31 | 2021-05-04 | 江苏万源新材料股份有限公司 | Antibacterial molecular sieve and preparation method thereof |
| CN113801378A (en) * | 2021-09-23 | 2021-12-17 | 沈阳市津浩科技有限公司 | Ionic liquid-loaded zeolite rubber reinforcing agent and preparation method thereof |
| CN113801378B (en) * | 2021-09-23 | 2023-01-17 | 沈阳市津浩科技有限公司 | Ionic liquid loaded zeolite rubber reinforcing agent and preparation method thereof |
| CN115025823A (en) * | 2022-05-23 | 2022-09-09 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Method for doping metal cations into zeolite |
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