CN1483318A - Stilbite carrier zine series inorganic germicide - Google Patents
Stilbite carrier zine series inorganic germicide Download PDFInfo
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- CN1483318A CN1483318A CNA021297002A CN02129700A CN1483318A CN 1483318 A CN1483318 A CN 1483318A CN A021297002 A CNA021297002 A CN A021297002A CN 02129700 A CN02129700 A CN 02129700A CN 1483318 A CN1483318 A CN 1483318A
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Abstract
The present invention provides a preparation method of stilbite carrier zinc series in organic antimicrobial agent. Said invented inorganic antibacterial agent is not limited by physical environment, has strong antibacterial action, good persistent availability, broad-spectrum antibacterial property and good compatibility for making other products. It can solve the product discoloration problem due to addition of antimicrobial agent, can raise the fineness of inorganic antimicrobial agent powder body, and can be uniformly distributed in the product, at the same time it can greatly reduce cost of inorganic antimicrobial agent.
Description
Affiliated technical field
The present invention relates to the preparation method of inorganic antiseptic, specifically, relate to the preparation method of stilbite carrier zine series inorganic germicide.
Background technology
Along with the growth of human material wealth and comprehensive progress of society, people more and more are concerned about environmental problem, to the problem that influences human health and quality of life that is caused by environment, are paid close attention to especially.Reduce and effectively prevent microorganism among the human settlement to human lives's interference and harm, alleviate the courses of infection and the disease popularity that cause thus and become social common recognition.In production place, public place and human settlement, these harm of environmental microorganism even jeopardize people's life.The control environment common measure of microorganism although produced positive effect as the organic class antibacterial agent sterilization of air cleaning, ultraviolet irradiation, ozone sterilization and use, also exists lasting effect poor, and the cost height has shortcoming such as foreign odor.Inorganic antiseptic is long because of lasting effect, and safety is good, uses advantage such as health to constitute the control environment method of microorganism and the measure of tool prospect.
Inorganic antiseptic generally is the pressed powder form, mainly as additive, and prepare all kinds of antibacterial products by combining, antibiotic by the practical application performance inorganic antiseptic of antibacterial product again, clean air and human body played function such as diseases prevention with the preparation technology of respective material.Use the antibacterial product of inorganic antiseptic preparation to mainly contain goods such as pottery, paper, cloth and plastics at present.Inorganic antiseptic can be divided into photocatalytic and metal ion tape carrier type two big classes by the principle of inhibition and kill bacteria, wherein the former is the semi-conductor type material, under UV-irradiation, semiconductor substance generation active oxygen etc. has the group of strong oxidation, the cytoactive of destroy microorganisms produces antimicrobial effect thus.Antibacterial agent just has antibacterial functions because only under the irradiation of ultraviolet light, so the scope of application is little, effect is unstable, and is difficult to detect and assess; Metal ion tape carrier type antibacterial agent mainly produces antibacterial action in ion slowly-releasing mode, is not subjected to the restriction of physical environment, and antibacterial action is strong, and lasting effect is good, tool broad spectrum activity and compatible advantage such as good with fabricated product.At present, metal ion tape carrier type inorganic antiseptic has become the main product of inorganic antiseptic on the market.But also have some problems in application process, the main performance both ways: one, the goods variable color is promptly adopted inorganic antiseptic to increase the weight of as the antibacterial product color of additive preparation, even can't be used.This is that the low institute of antibacterial agent self whiteness causes on the one hand, on the other hand, also is that most important factor then is that the excess of silver ion in the antibacterial agent is overflowed and formed the result of oxide with other component reaction of goods or self.Because in several metal ion species of preparation inorganic antiseptic, the antibacterial action of silver ion is the strongest, and received compoundly easily by inorganic matter carrier, so inorganic antiseptic overloading band silver ion constitutes; Silver ion not only easily causes the goods variable color, has also strengthened the cost of inorganic antiseptic simultaneously; Its two, the physical property of inorganic antiseptic powder, problems such as powder fineness, particle is thick because of existing, irrational distribution can't satisfy application requirements well.
Summary of the invention
The purpose of this invention is to provide a kind of do not influence goods color, antibiotic persistence improve, cheap and can satisfy the inorganic antiseptic of fabricated product well to the fine requirement of antibacterial agent powder granularity.
Foresite is the hydrous alumino silicates mineral, is a kind of of zeolite family mineral, by SiO
4And AlO
4Tetrahedron element is staggered to spacial framework.The same with other mineral of zeolite family, because the opening of crystal structure, foresite contains many sizes in nano-scale range, and duct that is evenly distributed and cavity, has huge specific surface area.In addition, often replaced by aluminium because of silicon in the foresite skeleton and to present the electricity price imbalance, in order to compensate positive charge, foresite can absorb alkali metal or alkaline-earth metal ions from surrounding environment, form ion exchangeable thus.The main aperture road of foresite mainly is distributed in the space both direction, and size distribution is 0.41-0.62nm and 0.27-0.57nm scope, and pore volume is 0.39cm
3/ cm
3Foresite is abundanter at the occurring in nature reserves, compares with the natural zeolite mineral that clinoptilolite and modenite etc. are main, and natural foresite purity is higher, generally more than 90%, whiteness is also higher, and generally more than 85%, these characteristics make it form application category widely.In the last few years, natural foresite had obtained more and more widely application at industrial department, and the specific aim process technology of foresite is also constantly carried out.
The present invention is a carrier with natural foresite, by compound with zinc ion and control its releasing degree and prepare the zinc series antibacterial agent, because zinc ion is more stable than silver ion, the effusion nondiscolouring, foresite whiteness height in addition, the antibacterial agent whiteness of preparation is also high, and therefore, the stilbite carrier inorganic antiseptic can solve the fabricated product discoloration problem of using silver-series antibacterial agent to cause preferably; In the present invention, ability was compound with zinc ion after stilbite carrier was finely ground to the micron order product by wet method, and therefore, the inorganic antiseptic product of preparation also satisfies the fabricated product performance requirement fine to the antibacterial agent powder granularity well.
The preparation method who realizes stilbite carrier zine series inorganic germicide of the present invention is:
Raw material selection:
1. natural foresite rock dust body, powder fineness 300-400 order.Wherein foresite content is 75%-85%, and the cation exchange total amount is 100-130mmol/100g;
2, calgon is mixed with the aqueous solution with deionized water, and solution concentration 20% is added as grinding aid when natural foresite rock dust body wet method fine grinding and used;
3, antimicrobial component is a zinc ion, uses technical pure other zinc nitrate of higher level and deionized water to be mixed with the aqueous solution and uses solution concentration 0.2M-2.5M;
4, flocculant is anionic or non-ionic polyacrylamide, is mixed with 0.1%-1.0% concentration and uses;
5, the final inorganic antiseptic that forms is made up of natural foresite and zinc ion, and wherein natural foresite content (weight ratio) is 92%-95%, zinc ion content 5%-8%.
The natural foresite powder of fineness 300-400 purpose makes its antibacterial agent as preparing carriers reach fineness by the extra-fine grinding that wet type stirs mill: less than 2 μ m content greater than 90%; Calgon adds when the wet method fine grinding, utilizes it to reduce effect such as ore pulp viscosity and plays the grinding aid effect, improves grinding efficiency.Realize receiving the purpose of zinc ion after the natural stilbite carrier extra-fine grinding with the zinc nitrate solution effect, and then play antibacterial action by the slowly-releasing zinc ion.Add in the solid-liquid suspension body of polyacrylamide in the batching after finishing the antimicrobial component exchange, its objective is the macromolecule bridging effect that utilizes it, realize intergranular flocculation, quicken Separation of Solid and Liquid.
The concrete steps of principle production process are:
One, at first in the natural foresite of fineness 300-400 order (kg): the ratio of deionized water volume (kg)=1: 1～2 takes by weighing two kinds of materials respectively, place wet type to stir in the extra-fine grinding system of mill, stir by agitator, and add the calgon that accounts for natural foresite 0.2%～0.8% and make slurry with high-speed stirred effect;
Two, start the extra-fine grinding system that wet type stirs mill, the slurry of making carried out grinding operation, up to levigate product granularity be less than 2 μ m content greater than 90% o'clock till;
Three, the levigate slurry with natural stilbite carrier material imports in the exchange reactor, metering slurry weight;
Four, in exchange reactor, add quantitative deionized water again, make to reach natural stilbite carrier material (kg) in the exchange reactor: the proportion requirement of the water yield (kg)=1: 2.5～4.
Five, in exchange reactor, mend zinc nitrate solution again, make to reach natural stilbite carrier material (kg) in the exchange reactor: the proportion requirement of solution amount (kg)=1: 4.5～5.5.The zinc nitrate solution amount of adding is for deducting original water yield according to this total zinc nitrate solution amount that requires to calculate, and the zinc nitrate amount that obtain solution drops into is determined according to following principle: remain in total solution, zinc nitrate concentration is 1.2～2M;
Six, utilize heater in the exchange reactor, the solid-liquid suspension body is heated to 95 ℃, moderate strength stirs 1.5～3h then, stops then stirring and suspended substance being reduced to room temperature;
Seven, in the agitator that the solid-liquid suspension body is housed, stir 3～10min, and in whipping process, add the anionic or the non-ionic polyacrylamide solution that account for natural stilbite carrier quantity of material 0.05%～0.1% slowly and make it form floccule;
Eight, suspended substance clear water is at the middle and upper levels extracted in siphon out, and the lower sediment thing places centrifuge or vacuum filter to filter and forms filter cake.
Nine, filter cake is placed the drying box of 90 ℃～120 ℃ of temperature be dried to water content less than 3%;
Ten, dried material is sent in the beater handled, make it to form even-grained powder, send into temperature again and be in 800 ℃～1000 ℃ the roaster, roasting 1～2.5 hour;
11, the thermal material that takes out from roaster is put into the metal hermetically sealed can immediately and is naturally cooled to room temperature;
12, directly divide bag hermetic package to become product by taking out cooled material in the metal hermetically sealed can.
Embodiment
Embodiment
1. natural stilbite carrier material 250kg, the deionized water 250kg with cation exchange total amount 100～130mmol/100g, fineness 300～400 orders, foresite content 75%-85% places wet type to stir in the extra-fine grinding system of mill, stir 15min by the agitator with high-speed stirred effect, the sodium hexametaphosphate solution 6.25kg that adds solution concentration 20% then makes slurry;
2. start the extra-fine grinding system that wet type stirs mill, the slurry of making is ground to less than 2 μ m content greater than till 90% o'clock according to the circulation grinding mode;
3. levigate slurry 400kg is imported in the exchange reactor, levigate slurry contains natural stilbite carrier material 200kg, deionized water 200kg;
4. in exchange reactor, add deionized water 400kg, make that the ratio of natural stilbite carrier material (kg) and the water yield (kg) is 1: 3 in the exchange reactor;
5. to mend concentration again in exchange reactor be 3.75M, by the zinc nitrate solution 400kg of deionized water preparation, make to reach natural stilbite carrier material (kg) in the exchange reactor: solution amount (kg)=1: 5, zinc nitrate solution concentration are 1.5M;
6. utilize the heater in the exchange reactor, the solid-liquid suspension body is heated to 95 ℃, moderate strength stirred 2 hours then.Stop again stirring and suspended substance being reduced to room temperature;
7. again suspended substance is stirred 5min in exchange reactor, and in whipping process, add the non-ionic polyacrylamide aqueous solution 6kg of solution concentration 1% slowly, form floccule;
8. suspended substance clear water is at the middle and upper levels extracted in siphon out, and the lower sediment thing places centrifuge or vacuum filter to filter and forms filter cake.Again filter cake is placed the drying box of 90 ℃～120 ℃ of temperature to be dried to water content less than 3%;
9. dried material is sent in the beater and handled, make it to form even-grained powder;
10. it is in 800 ℃～1000 ℃ the roaster that dried powder material is sent into temperature, roasting 1.5 hours;
11. the thermal material that takes out from roaster is put into the metal hermetically sealed can immediately and is naturally cooled to room temperature;
12. directly divide bag hermetic package to become product by taking out cooled material in the metal hermetically sealed can.
The performance of the stilbite carrier zine series inorganic germicide of making by embodiment is shown in table 1, and its anti-microbial property of making the antibacterial styrene-acrylate latex paint of additive preparation is shown in table 2.The result shows that it has stronger antibacterial functions.
The anti-microbial property table 1 of zinc series antibacterial agent of the present invention
| Bacteria name | Escherichia coli | Staphylococcus aureus | |||||
| Antibacterial agent concentration (μ g/ ml) | ??100 | ??200 | ??400 | ??500 | ??200 | ??400 | ??500 |
| Contact sterilization rate (%) | ??0 | ??0 | ??80 | ??99.9 | ??0 | ??70 | ??99.9 |
Add the anti-microbial property table 2 of zinc series antibacterial agent coating of the present invention
Adopt the stilbite carrier zine series inorganic germicide of the inventive method preparation, be not subjected to the restriction of physical environment, and antibacterial action is strong, lasting effect is good, tool broad spectrum activity and compatible advantage such as good with fabricated product, particularly solved antibacterial agent to the goods discoloration problem, improved the fineness of inorganic antiseptic powder, in goods, be more evenly distributed, and can satisfy application requirements well, greatly reduce the cost of inorganic antiseptic simultaneously.
Claims (3)
1, a kind of preparation method of stilbite carrier zine series inorganic germicide is characterized in that: raw material selection: (1) natural foresite rock dust body, powder fineness 300～400 orders.Wherein foresite content is 75%-85%, and the cation exchange total amount is 100～130mmol/100g; (2) calgon is mixed with the aqueous solution with deionized water, and solution concentration 20% is added as grinding aid when natural foresite rock dust body wet method fine grinding and used; (3) antimicrobial component is a zinc ion, uses technical pure other zinc nitrate of higher level and deionized water to be mixed with the aqueous solution and uses solution concentration 0.2M～2.5M; (4) flocculant is anionic or non-ionic polyacrylamide, is mixed with 0.1%～1.0% concentration and uses; (5) the final inorganic antiseptic that forms is made up of natural foresite and zinc ion, and wherein natural foresite content (weight ratio) is 92%～95%, zinc ion content 5%～8%.
2, a kind of preparation method of stilbite carrier zine series inorganic germicide, it is characterized in that: the step of production process is: (1) is at first in the natural foresites of fineness 300～400 orders (kg): the ratio of deionized water volume (kg)=1: 1～2 takes by weighing two kinds of materials respectively, place wet type to stir in the extra-fine grinding system of mill, stir by agitator, and add the calgon that accounts for natural foresite 0.2%～0.8% and make slurry with high-speed stirred effect; (2) start the extra-fine grinding system that wet type stirs mill, the slurry of making carried out grinding operation, up to levigate product granularity be less than 2 μ m content greater than 90% o'clock till; (3) the levigate slurry with natural stilbite carrier material imports in the exchange reactor, metering slurry weight; (4) in exchange reactor, add quantitative deionized water again, make to reach natural stilbite carrier material (kg) in the exchange reactor: the proportion requirement of the water yield (kg)=1: 2.5～4.(5) in exchange reactor, mend zinc nitrate solution again, make to reach natural stilbite carrier material (kg) in the exchange reactor: the proportion requirement of solution amount (kg)=1: 4.5～5.5.The zinc nitrate solution amount of adding is for deducting original water yield according to this total zinc nitrate solution amount that requires to calculate, and the zinc nitrate amount that obtain solution drops into is determined according to following principle: remain in total solution, zinc nitrate concentration is 1.2～2M; (6) utilize heater in the exchange reactor, the solid-liquid suspension body is heated to 95 ℃, moderate strength stirs 1.5～3h then, stops then stirring and suspended substance being reduced to room temperature; (7) in the agitator that the solid-liquid suspension body is housed, stir 3～10min, and in whipping process, add the anionic or the non-ionic polyacrylamide solution that account for natural stilbite carrier quantity of material 0.05%～0.1% slowly and make it form floccule; (8) suspended substance clear water is at the middle and upper levels extracted in siphon out, and the lower sediment thing places centrifuge or vacuum filter to filter and forms filter cake; (9) filter cake is placed the drying box of 90 ℃～120 ℃ of temperature be dried to water content less than 3%; (10) dried material is sent in the beater handled, make it to form even-grained powder, send into temperature again and be in 800 ℃～1000 ℃ the roaster, roasting 1～2.5 hour; (11) thermal material that takes out from roaster is put into the metal hermetically sealed can immediately and is naturally cooled to room temperature; (12) directly divide bag hermetic package to become stilbite carrier zine series inorganic germicide product of the present invention by taking out cooled material in the metal hermetically sealed can.
3, according to the preparation method of claim 1 and 2 described stilbite carrier zine series inorganic germicides, it is characterized in that: (1) places wet type to stir in the extra-fine grinding system of mill natural stilbite carrier material 250kg, the deionized water 250kg of cation exchange total amount 100～130mmol/100g, fineness 300～400 orders, foresite content 75%～85%, stir 15min by the agitator with high-speed stirred effect, the sodium hexametaphosphate solution 6.25kg that adds solution concentration 20% then makes slurry; (2) start the extra-fine grinding system that wet type stirs mill, the slurry of making is ground to less than 2 μ m content greater than till 90% o'clock according to the circulation grinding mode; (3) levigate slurry 400kg is imported in the exchange reactor, levigate slurry contains natural stilbite carrier material 200kg, deionized water 200kg; (4) in exchange reactor, add deionized water 400kg, make that the ratio of natural stilbite carrier material (kg) and the water yield (kg) is 1: 3 in the exchange reactor; (5) to mend concentration again in exchange reactor be 3.75M, by the zinc nitrate solution 400kg of deionized water preparation, make to reach natural stilbite carrier material (kg) in the exchange reactor: solution amount (kg)=1: 5, zinc nitrate solution concentration are 1.5M; (6) utilize heater in the exchange reactor, the solid-liquid suspension body is heated to 95 ℃, moderate strength stirred 2 hours then.Stop again stirring and suspended substance being reduced to room temperature; (7) again suspended substance is stirred 5min in exchange reactor, and in whipping process, add the non-ionic polyacrylamide aqueous solution 6kg of solution concentration 1% slowly, form floccule; (8) suspended substance clear water is at the middle and upper levels extracted in siphon out, and the lower sediment thing places centrifuge or vacuum filter to filter and forms filter cake.Again filter cake is placed the drying box of 90 ℃～120 ℃ of temperature to be dried to water content less than 3%; (9) dried material is sent in the beater handled, make it to form even-grained powder; (10) to send into temperature be in 800 ℃～1000 ℃ the roaster to dried powder material, roasting 1.5 hours; (11) thermal material that takes out from roaster is put into the metal hermetically sealed can immediately and is naturally cooled to room temperature; (12) directly divide bag hermetic package to become the stilbite carrier zine series inorganic germicide product by taking out cooled material in the metal hermetically sealed can.
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|---|---|---|---|
| CN 02129700 CN1283154C (en) | 2002-09-16 | 2002-09-16 | Stilbite carrier zine series inorganic germicide |
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|---|---|---|---|
| CN 02129700 CN1283154C (en) | 2002-09-16 | 2002-09-16 | Stilbite carrier zine series inorganic germicide |
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| Publication Number | Publication Date |
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| CN1483318A true CN1483318A (en) | 2004-03-24 |
| CN1283154C CN1283154C (en) | 2006-11-08 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101884338A (en) * | 2010-07-05 | 2010-11-17 | 广西师范大学 | Antibacterial agent containing copper, silver and zinc antibacterial metal ions, and preparation method thereof |
| CN101023751B (en) * | 2006-02-22 | 2011-04-27 | 株式会社品燃洁而美客 | Antimicrobial zeolite and antimicrobial composition |
| CN101265112B (en) * | 2008-04-17 | 2011-08-31 | 上海伊索热能技术有限公司 | Suspending agent of mica mineral in water solution |
| CN101708879B (en) * | 2009-08-11 | 2012-02-01 | 上海沃杉化工有限公司 | Inorganic-organic composite flocculating agent and preparation method thereof |
| CN104186545A (en) * | 2014-08-09 | 2014-12-10 | 三河市京纳环保技术有限公司 | Novel large-scale simple preparation method of zeolite zinc-loaded inorganic antibacterial agent |
| CN111000114A (en) * | 2020-01-08 | 2020-04-14 | 汪博文 | Preparation method of inorganic antibacterial agent for feed |
| CN112724579A (en) * | 2020-10-29 | 2021-04-30 | 天津金发新材料有限公司 | Antibacterial low-odor polypropylene composite material for automotive interior and preparation method thereof |
-
2002
- 2002-09-16 CN CN 02129700 patent/CN1283154C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101023751B (en) * | 2006-02-22 | 2011-04-27 | 株式会社品燃洁而美客 | Antimicrobial zeolite and antimicrobial composition |
| CN101265112B (en) * | 2008-04-17 | 2011-08-31 | 上海伊索热能技术有限公司 | Suspending agent of mica mineral in water solution |
| CN101708879B (en) * | 2009-08-11 | 2012-02-01 | 上海沃杉化工有限公司 | Inorganic-organic composite flocculating agent and preparation method thereof |
| CN101884338A (en) * | 2010-07-05 | 2010-11-17 | 广西师范大学 | Antibacterial agent containing copper, silver and zinc antibacterial metal ions, and preparation method thereof |
| CN104186545A (en) * | 2014-08-09 | 2014-12-10 | 三河市京纳环保技术有限公司 | Novel large-scale simple preparation method of zeolite zinc-loaded inorganic antibacterial agent |
| CN111000114A (en) * | 2020-01-08 | 2020-04-14 | 汪博文 | Preparation method of inorganic antibacterial agent for feed |
| CN112724579A (en) * | 2020-10-29 | 2021-04-30 | 天津金发新材料有限公司 | Antibacterial low-odor polypropylene composite material for automotive interior and preparation method thereof |
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|---|---|
| CN1283154C (en) | 2006-11-08 |
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