CN1345537A - Silver carried complex ion palygorskite type inorganic germicide - Google Patents

Silver carried complex ion palygorskite type inorganic germicide Download PDF

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Publication number
CN1345537A
CN1345537A CN 00124957 CN00124957A CN1345537A CN 1345537 A CN1345537 A CN 1345537A CN 00124957 CN00124957 CN 00124957 CN 00124957 A CN00124957 A CN 00124957A CN 1345537 A CN1345537 A CN 1345537A
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China
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silver
palygorskite
complex ion
organic complex
colored organic
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CN1177534C (en
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郑自立
胡发社
程海丽
杨飞华
郑桂兵
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BEIJING ACADEMY OF ARCHITECTURAL MATERIAL SCIENCES
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BEIJING ACADEMY OF ARCHITECTURAL MATERIAL SCIENCES
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Priority to CNB001249576A priority Critical patent/CN1177534C/en
Publication of CN1345537A publication Critical patent/CN1345537A/en
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Abstract

The invention relates to a preparation method for inorganic antimicrobial agent that includes bearer and antibiosis component. Mineral lassallite is said bearer and silver organic complex ion with stable physical and chemical characters is as said antibiosis component. Technological process includes three steps there are preparation of silver organic complex ion, acidizing and activating treatment and preparation of antimicrobial agent. The invented inorganic antimicrobial agent provides features of notable durability in germ resistance and stability in high temperature resistant.

Description

Silver carried complex ion palygorskite type inorganic germicide
The present invention relates to a kind of preparation method of inorganic antiseptic, specifically, relating to the palygorskite is carrier, with the silver-colored organic complex ion preparation method that is the inorganic antiseptic of antibacterial components.
Antibacterial agent is meant and can suppresses growth of microorganism breeding or with its material of killing, antibacterial agent can be divided into organic antibacterial agent and inorganic antiseptic two major types by its carrier, inorganic antiseptic is that the inorganic matter that adopts cavernous zeolite, atlapulgite etc. to have ion-exchange performance is a carrier mostly, utilize antibiotic, the bactericidal actions of the antimicrbial power that metal ion or oxide, complex compound or some catalysis materials had performance such as contained silver, copper, zinc, it is strong to make it have antibiotic property, heat-resistant stable is good, the characteristic that safety is good.Inorganic antiseptic is in Japan at present, be widely used in domestic ceramics in the western developed countries such as the U.S., the every field of ornament materials and daily living article, inorganic antiseptic is because its good endurance, to human body and environmental safety height, pay attention to the inorganic antiseptic development in the world since the late nineteen eighties, the base material that is used to make inorganic antiseptic mostly was cavernous zeolite in the past, atlapulgites etc. have the carrier of ion exchangeable, but because cavernous zeolite, atlapulgite all exists specific surface area little, bad dispersibility, so that a little less than its absorption property, influence antibacterial components absorption, the application of antibacterial agent and effect are restricted.Appearance along with NACF with high-specific surface area, the inorganic antiseptic that with the NACF is carrier is developed rapidly, but because NACF cost height, use the inorganic antiseptic price of its making also to raise, therefore its range of application is affected,, improves performances such as inorganic antiseptic self adsorption capacity, dispersiveness simultaneously for reducing cost, the utilization that begins one's study is a carrier with the palygorskite, is the inorganic antiseptic of antibacterial components with the silver ion.This inorganic antiseptic is owing to utilized palygorskite to be carrier, reduced cost significantly, yet the argent ion as antibacterial components easily is converted into argent in antibacterial agent, argent can be converted into silver oxide again, thereby influence the antibiotic persistence of inorganic antiseptic, the particularly application in the material that color is had relatively high expectations.
Purpose of the present invention is exactly to prepare a kind of antibiotic persistence and cheap inorganic antiseptic of improving.
Inorganic antiseptic of the present invention is to be carrier with layer chain silicate clay mineral palygorskite, it has big specific surface area, very strong adsorptivity and dispersiveness, with the stable silver-colored organic complex ion of physical and chemical performance is that antibacterial components is made, and its technological process comprises preparation section three parts of preparation, palygorskite acid activation processing and the antibacterial agent of silver-colored organic complex ion:
(1) preparation of silver-colored organic complex ion:
Selecting chemical pure organic matter 2.2 ` bipyridyls and silver soluble saline solution for use, is 0.5-2 with the mole ratio: 1 mix to add in the reaction vessel, and under 40-80 ℃ of temperature, stirring reaction 0.5-2 hour, being cooled to normal temperature at last, to make silver-colored organic complex ion standby.
(2) palygorskite acid activation treatment process is as follows:
Select for use purity greater than 90% earthy palygorskite through crushing grinding to less than 140 orders, with concentration be the hydrochloric acid of 0.5-2M, with solid: liquid=1: 1-5 mixes the back and adds in the reactor, under 80-100 ℃ of temperature, stirring reaction 1-2h carries out acid activation to palygorskite, then centrifugal dehydration in centrifuge, washing, put into baking oven afterwards, under 100-150 ℃ of condition, dry, be ground to granularity at last, make the acid activation palygorskite carrier that absorption property has had obvious improvement less than 200 orders.
(3) preparation section of antibacterial agent is as follows:
The silver-colored organic complex ion that makes in (1) is mixed with the solution that concentration is 0.001-0.01M, with the acid activation palygorskite carrier that makes in (2) with solid: liquid=1: put into reactor after 15-25 mixes, under 30-60 ℃ condition, carried out stirring reaction 5-10 hour.Then reactant liquor is put into centrifuge and carries out centrifugal washing, remove unnecessary silver-colored organic complex ion after, carry out natural air drying or in baking oven, dry, be ground to granularity at last less than 200 purpose powder, promptly make palygorskite type inorganic anti-biotic agent of the present invention.
Inorganic antibacterial agent carrier palygorskite described in the present invention can replace with mineral sepiolite of the same clan.
The best preparation method who realizes palygorskite type inorganic anti-biotic agent of the present invention is:
At first selecting chemical pure organic matter 2.2 ` bipyridyl and silver nitrate aqueous solutions for use, is mix to add in reaction vessel at 1: 1 with mole ratio, under 60 ℃ of temperature, and stirring reaction 1 hour, being cooled to normal temperature, to make silver-colored organic complex ion standby.
Then palygorskite is carried out the acid activation treatment process, promptly select for use purity greater than 90% earthy palygorskite through crushing grinding to less than 140 orders, with concentration be the hydrochloric acid of 1M, with solid: liquid=mix back add in reactor at 1: 3, under 95 ℃ of temperature condition, stirring reaction 1.5h carries out acid activation to palygorskite to be handled, centrifugal dehydration in centrifuge then, washing, put into baking oven afterwards, under 150 ℃ of conditions, dry, be ground to granularity at last less than 200 orders, making absorption property has had the acid activation palygorskite carrier of obvious improvement, palygorskite carrier after then acid activation being handled and concentration be the silver-colored organic complex deionized water solution of 0.005M to consolidate: put into reactor after liquid=1: 20 mixes, under 50 ℃ condition, carried out stirring reaction 6 hours.Then reactant liquor is put into centrifuge and carry out centrifugal washing, after removing unnecessary silver-colored organic complex ion, carry out natural air drying or in baking oven, dry, be ground to granularity at last, promptly make silver carried complex ion palygorskite type inorganic germicide of the present invention less than 200 purpose powder.
Silver carried complex ion palygorskite type inorganic germicide of the present invention is through the anti-microbial property experiment of Shijingshan District, Beijing health and epidemic prevention station, and experiment shows that this antibacterial agent has good antibacterial performance.Silver carried complex ion palygorskite type inorganic germicide heat-resistant stable of the present invention is good, heats nondiscolouring in 1 hour down and still has tangible anti-microbial property at 800 ℃; The antibiotic persistence of this inorganic antiseptic is good, ultraviolet irradiation or 2 months illumination color no changes; Inorganic antiseptic of the present invention has no adverse effect to the health of human body; And with market on be that the inorganic antiseptic of carrier is compared with zeolite, atlapulgite or charcoal fiber, cheap, have remarkable economic efficiency.In addition, as palygorskite, the sepiolite of antibacterial agent carrier, its distinctive layer chain crystal structure makes its crystals be distributed with the zeolite cavity structure of very growing, and acicular aggregate has the loose structure of interweaving, make it show distinctive bigger serface, strong adsorptivity.Palygorskite, sepiolite have very strong dispersive property as clay mineral simultaneously, can be scattered in equably in the various Material Useds.Inorganic antiseptic of the present invention can be used as filler or smears the every field that material is applied to ornament materials, medical material, reaches daily living article.

Claims (6)

1, a kind of preparation method of palygorskite type inorganic anti-biotic agent, it is characterized in that: be to be carrier with layer chain silicate clay mineral palygorskite, with the stable silver-colored organic complex ion of physical and chemical performance is that antibacterial components is made, and its technological process comprises the preparation section three parts composition of preparation, palygorskite acid activation processing and the antibacterial agent of silver-colored organic complex ion.
2, the preparation of the silver-colored organic complex ion of inorganic antiseptic according to claim 1, it is characterized in that: select chemical pure organic matter 2.2 ` bipyridyls and silver soluble saline solution for use, with the mole ratio is 0.5-2: 1 mixes in the adding reaction vessel, under 40-80 ℃ of temperature, stirring reaction 0.5-2 hour, be cooled to normal temperature at last and make silver-colored organic complex ion.
3, the preparation section of antibacterial agent according to claim 1, it is characterized in that: silver-colored organic complex ion is mixed with the solution that concentration is 0.001-0.01M, with acid activation palygorskite carrier with solid: liquid=1: put into reactor after 15-25 mixes, under 30-60 ℃ condition, carried out stirring reaction 5-10 hour.Then reactant liquor is put into centrifuge and carries out centrifugal washing, remove unnecessary silver-colored organic complex ion after, carry out natural air drying or in baking oven, dry, be ground to granularity at last less than 200 purpose powder, promptly make palygorskite type inorganic anti-biotic agent of the present invention.
4, inorganic antibacterial agent carrier palygorskite according to claim 1 is characterized in that: palygorskite can replace with mineral sepiolite of the same clan.
5, the preparation of the silver-colored organic complex ion of inorganic antiseptic according to claim 2, it is characterized in that: select chemical pure organic matter 2.2 ` bipyridyl and silver nitrate aqueous solutions for use, with mole ratio is that mixing in 1: 1 adds in the reaction vessel, under 60 ℃ of temperature, stirring reaction 1 hour, being cooled to normal temperature, to make silver-colored organic complex ion standby.
6, the preparation section of antibacterial agent according to claim 3, it is characterized in that: the palygorskite carrier after acid activation is handled and concentration be the silver-colored organic complex deionized water solution of 0.005M to consolidate: put into reactor after liquid=1: 20 mixes, under 50 ℃ condition, carried out stirring reaction 6 hours.Then reactant liquor is put into centrifuge and carry out centrifugal washing, after removing unnecessary silver-colored organic complex ion, carry out natural air drying or in baking oven, dry, be ground to granularity at last, promptly make silver carried complex ion palygorskite type inorganic germicide of the present invention less than 200 purpose powder.
CNB001249576A 2000-09-27 2000-09-27 Silver carried complex ion palygorskite type inorganic germicide Expired - Fee Related CN1177534C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100403907C (en) * 2004-05-30 2008-07-23 云南大学 Inorganic bactericidal agent and its use
CN105289471A (en) * 2015-11-19 2016-02-03 兰州坤仑环保科技有限公司 Antibacterial attapulgite mineral drying agent for food package
CN106135275A (en) * 2016-06-24 2016-11-23 湘潭大学 A kind of preparation method of the sepiolite antimicrobial powder of organically-modified and load silver ion
CN107441580A (en) * 2016-05-03 2017-12-08 B·布莱恩·阿维图姆股份公司 Medical treatment device including antimicrobial surface coating and the method for the microorganism on the surface for controlling this device
CN112315976A (en) * 2020-11-16 2021-02-05 山西大同大学 Injectable antibacterial composite hydrogel crosslinked by silver-loaded attapulgite, and preparation method and application thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100403907C (en) * 2004-05-30 2008-07-23 云南大学 Inorganic bactericidal agent and its use
CN105289471A (en) * 2015-11-19 2016-02-03 兰州坤仑环保科技有限公司 Antibacterial attapulgite mineral drying agent for food package
CN107441580A (en) * 2016-05-03 2017-12-08 B·布莱恩·阿维图姆股份公司 Medical treatment device including antimicrobial surface coating and the method for the microorganism on the surface for controlling this device
CN106135275A (en) * 2016-06-24 2016-11-23 湘潭大学 A kind of preparation method of the sepiolite antimicrobial powder of organically-modified and load silver ion
CN112315976A (en) * 2020-11-16 2021-02-05 山西大同大学 Injectable antibacterial composite hydrogel crosslinked by silver-loaded attapulgite, and preparation method and application thereof
CN112315976B (en) * 2020-11-16 2022-10-11 山西大同大学 Injectable antibacterial composite hydrogel crosslinked by silver-loaded attapulgite, and preparation method and application thereof

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