CN1358441A - Copper-carried montmorillonite solid and liquid disinfectant and preparation process - Google Patents

Copper-carried montmorillonite solid and liquid disinfectant and preparation process Download PDF

Info

Publication number
CN1358441A
CN1358441A CN 01145558 CN01145558A CN1358441A CN 1358441 A CN1358441 A CN 1358441A CN 01145558 CN01145558 CN 01145558 CN 01145558 A CN01145558 A CN 01145558A CN 1358441 A CN1358441 A CN 1358441A
Authority
CN
China
Prior art keywords
copper
montmorillonite
preparation
water
sodium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 01145558
Other languages
Chinese (zh)
Inventor
叶瑛
夏枚生
周玉航
沈忠悦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN 01145558 priority Critical patent/CN1358441A/en
Publication of CN1358441A publication Critical patent/CN1358441A/en
Pending legal-status Critical Current

Links

Landscapes

  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention discloses a copper-carried montmorillonite solid or suspension liquid germicide and its preparation method. It is characterized by that it is a montmorillonite containing exchangeable copper ion, and the copper element content being in the montmorillonite is 0.5-6.5 wt%, and its preparation method includes the following steps: utilizing the ion exchange capacity of clay mineral to implant the Cu(2+) with bactericidal and fungicidal power into sodium base montmorillonite lattice to obtain copper-carried montmorillonite contaiing active copper ions, drying-grinding or spraying-drying to obtain solid powder or making it into suspension liquid preparation. The invented germicide possesses xtensive application fields and its production process is simple and cost is low.

Description

Copper-loaded montmorillonite is solid-state with suspension liquid bactericide and preparation method thereof
Technical field
It is solid-state with suspension liquid bactericide and preparation method thereof to the present invention relates to a kind of copper-loaded montmorillonite.
Background technology
Copper-based fungicide, fungicide are used widely in fields such as agricultural, aquacultures.Compare with organic synthesis bactericide, fungicide, the inorganic compound of copper has advantages such as safe, that antibacterial range is wide, the term of validity is long, as copper sulphate, Kocide SD etc.But on using, directly use copper-containing compound need expend a large amount of copper, be unfavorable for reducing production costs, in addition, excessive copper can be residual in soil, causes environmental pollution.The copper-loaded montmorillonite that the present invention relates to utilizes the slowly releasing effect of clay mineral, and the remaining electric charge of copper-loaded back mineral surfaces, has improved the biologically active of copper ion greatly, is the important improvement to existing copper-based fungicide, fungicide.Compare with traditional copper compound type antibacterial agent, it only contains a little copper element, and antibiotic effect obviously strengthens, and less to the negative effect of environment.
Summary of the invention
It is solid-state with suspension liquid bactericide and preparation method thereof to the purpose of this invention is to provide a kind of copper-loaded montmorillonite.
Bactericide is a kind of montmorillonite that contains commutative copper ion, and by weight percentage, the content of copper in montmorillonite is 0.5~6.5%.
Preparation method's step is as follows:
1) adopts na-montmorillonite; Perhaps, make na-montmorillonite through following steps through separating calcium base, the magnesium base montmorillonite of purifying:
A) montmorillonite adds water and stirs together with the sodium salt that is equivalent to the about 5-15% of ore weight, makes the suspension ore pulp of concentration about 10%;
B) under 40~100 ℃ of temperature, the ion-exchange reactions time is no less than six hours, during stir frequently;
C) behind the centrifugal or filtering means dehydration, water cleans 1-2 time;
2) add the mantoquita that copper content is equivalent to ore weight 2-10%, or its water-containing crystal salt, add the ore pulp that water is made concentration about 10% again, stir the back under 40~100 ℃ of temperature, the ion-exchange reactions time is no less than six hours, during stir frequently;
3) behind the centrifugal or filtering means dehydration, clean 1-2 time, and dehydration again;
4) the step 3) gains are cool naturally shines dryly, or dries being lower than under 80 ℃ of temperature, selects for use suitable equipment to be ground to less than 300 orders, obtains water content less than 10% powder, stand-by;
Perhaps: the step 3) gains add maximum 5% dispersant, add water and stir, and make the ore pulp of 10-30%, select for use suitable spray drying device to carry out drying, and the spray dryer EAT should be controlled at 150~180 ℃ of scopes; The discharging opening temperature is no more than 70 ℃, obtains water content less than 10% powder, and is stand-by;
Perhaps: step (3) gains add maximum 5% dispersant, add water and stir, and make the suspension of debita spissitudo again, and are stand-by.
Said sodium salt is sodium chloride, sodium nitrate, sodium sulphate.Mantoquita is copper sulphate, copper chloride, copper nitrate.Dispersant is a sodium tripolyphosphate, tetrasodium pyrophosphate, one or more in the sodium lignosulfonate.
Advantage of the present invention is:
1) utilize the cation exchange capacity (CEC) of natural montmorillonite to carry copper ion, production cost is low;
2) copper content is low in bactericide, the fungicide, has reduced the environment residual quantity;
3) slow-release capability of montmorillonite is renderd a service lastingly product sterilization, antifungal;
4) safe in utilization, applied widely.
Embodiment
The raw material that the present invention uses is the natural montmorillonite of purifying through separating, and has another name called bentonite.The purification technique of montmorillonite is well-known, and it comprises that pulverizing, making beating make suspension, classification and collect approximately steps such as particle less than 2 μ.This highly purified montmorillonite is the clay mineral of a kind of light green color, light yellow tool layered crystal structure.Separate purification process and can select conventional mining equiment for use.
Be applicable to that dispersant requirement of the present invention is not very strict.The dispersant of recommending to use is a sodium tripolyphosphate, one or more in tetrasodium pyrophosphate and the sodium lignosulfonate.The purpose that adds dispersant is the viscosity that reduces slurry, makes the atomized drying of high concentration slurry become possibility, thereby reduces energy consumption for drying; In addition, dispersant can increase the stability of suspension, delays its precipitation.
In manufacturing process of the present invention, it is not very strict that the water yield that relevant step is added requires, and under the prerequisite that equipment such as stirring, mixing and atomized drying can run well, should reduce water, to reduce production costs as far as possible.Stirring and mixing can be selected conventional equipment for use, and the time limit of mixing is advisable can form obviously uniform slurry.
Ion-exchange reactions is carried out in two steps, and the first step is used sodium salt solution, makes the Na in the solution +Ca in the ion exchange montmorillonite mineral lattice 2+, Mg 2+With other interlayer cation, said sodium salt is sodium chloride, sodium nitrate, sodium sulphate.Second step was used copper salt solution, made the Cu in the solution 2+Na in the ion exchange montmorillonite mineral lattice +With other interlayer cation, said mantoquita is copper sulphate, copper chloride, copper nitrate.The requirement of sodium salt and mantoquita usage amount is not very strict, and generally speaking, the sodium salt consumption is not less than 8% of montmorillonite dry weight, and copper content is not less than 2.5% of montmorillonite dry weight and is advisable in the mantoquita.
Copper-loaded later montmorillonite can be selected the conventional drying method for use, and baking temperature should be above 80 ℃; Also can the natural drying drying at the arid climate environment, again it is ground to granularity and is not more than 300 orders.
The most handy spray drying device of slurry carries out drying, and the spray dryer EAT is controlled at 150~180 ℃ of scopes, and the discharging opening temperature is no more than 70 ℃.Spray dried products is a kind of runny pressed powder.Being used for spray drying device of the present invention is routinely, and technical is well-known.
Preparation of the present invention has two types, and water content is less than<10% pressed powder and contain the suspension of dispersant.Wherein the solid powder preparation copper content is generally between 2~3%.When dilute with water, swelling and mechanical agitation by montmorillonite are easy to form uniform aqueous dispersion.
Embodiment 1: the preparation of granular pattern copper-loaded montmorillonite bactericide, fungicide
1.1 somewhere ca-montmorillonite lump ore separates the back purity of purifying and reaches more than 95%.Take by weighing 100g purification ore, add water 900ml, stir and make suspension.
1.2 add 10g NaCl, the back that stirs (needing 20 minutes approximately) is heated to about 60 ℃, ion-exchange reactions six hours, during stir frequently.
1.3 centrifugation, supernatant liquor inclines.Add water 900ml again, stir, centrifugation, supernatant liquor inclines.Repeat 1-2 time.Again make volume and be one liter suspension.
1.4 add CuSO 45H 2O 9g fully stirs, be heated to about 60 ℃, ion-exchange reactions six hours, during stir frequently.
1.5 centrifugation, supernatant liquor inclines.Add water 900ml again, stir, centrifugation, supernatant liquor inclines.
1.6 add 5 gram sodium tripolyphosphates, add water 300ml, fully stir, make to mix, be no more than atomized drying under 180 ℃ of temperature condition at EAT, obtain water content less than 10% powder, stand-by.
The copper-loaded montmorillonite bactericide, the fungicide copper content that make by above-mentioned steps are 2.6%.
Embodiment 2: the anti-microbial property of copper-loaded montmorillonite
2.1 bacterial classification
Escherichia coli, staphylococcus aureus (providing) by Zhejiang Microbe Inst.
2.2 microorganism culture experiment
The bacterium incubated overnight: bacterium is in overnight incubation under the aerobic situation (about 12 hours), 37 ℃ of temperature, and culture fluid is made suspension with centrifugation washed twice (10,000 change) with distilled water flushing, and bacterial content is 10 4/ ml~10 5/ ml.
Add 0,1,2.5,5,10 and 20 milligram of copper-loaded montmorillonite in 100ml distilled water respectively, vibration makes to mix, and shaken cultivation is 24 hours then, 37 ℃ of cultivation temperature.
Growth analysis: respectively after 0,2,4,6 and 24 hour, in above-mentioned mixed liquor, take out 0.1ml solution, dilute and be finite concentration, dull and stereotypedly cultivated 37 ℃ of temperature 24 hours.Carry out plate count then.Each sample is done three parallel cultivation countings, averages.
2.3 bactericidal effect (see Table 1 and table 2)
Table 1: Escherichia coli count results in the culture fluid (individual/ml)
?0mg 1mg 2.5mg 5mg 10mg 20mg
?0h ?9.2×10 4 8.35×10 4 8.35×10 4 8.35×10 4 8.35×10 4 8.35×10 4
?2h ?9.3×10 4 5.2×10 4 3.0×10 4 1.5×10 4 6.4×10 3 0
?4h ?8.65×10 4 1.6×10 4 8.9×10 3 70 0 0
?6h ?8.2×10 4 7.3×10 2 0 0 0 0
?24h ?8.35×10 4 0 0 0 0 0
Table 2: staphylococcus aureus count results in the culture fluid (individual/ml)
?0mg 1mg ?2.5mg ?5mg ?10mg ?20mg
?0h ?1.19×10 5 1.19×10 5 ?1.19×10 5 ?1.19×10 5 ?1.19×10 5 ?1.19×10 5
?2h ?9.8×10 4 8.9×10 4 ?5.2×10 4 ?9.7×10 3 ?0 ?0
?4h ?9.37×10 4 1.2×10 4 ?6.1×10 3 ?0 ?0 ?0
?6h ?7.5×10 4 9.5×10 2 ?0 ?0 ?0 ?0
?24h ?6.35×10 4 0 ?0 ?0 ?0 ?0
First behavior of table 1 and table 2 (contains bacterium 10 for each hundred milliliters 4~10 5The weight of individual/copper-loaded montmorillonite of ml) adding in the distilled water, first classifies as and adds the time of cultivating behind the copper-loaded montmorillonite, and all the other be dull and stereotyped cultivation counting statistics result (mean values of three parallel sample).
Experimental result shows that copper-loaded montmorillonite all has the very strong ability of killing for Gram-negative bacteria (Escherichia coli) and gram-positive bacteria (Staphylococcus aureus).When using 20mg copper-loaded montmorillonite (concentration is 200mg/L) in the 100ml water body, can in 2 hours, this two bacterioid be killed fully.
The invention provides a kind of is the bactericide, fungicide and preparation method thereof of active component with the copper-loaded montmorillonite.The raw material sources that this invention relates to are abundant, and preparation method's technological process is simple, and low production cost is easy to promotion and implementation.The bactericide that makes based on the present invention, sterilization and the antimicrobial treatment that fungicide can be widely used in environment, public utility and commodity, the feed addictive of prevention, control animal alimentary canal infectious disease, the antibiotic filler of industries such as plastics, paper, cosmetics, textile, the preparation of antibiotic paint and antibacterial film etc.

Claims (5)

1. the solid-state and suspension liquid bactericide of copper-loaded montmorillonite is characterized in that it is a kind of montmorillonite that contains commutative copper ion, and by weight percentage, the content of copper in montmorillonite is 0.5~6.5%.
2. the solid-state preparation method with the suspension liquid bactericide of a copper-loaded montmorillonite is characterized in that its step is as follows:
1) adopts na-montmorillonite; Perhaps, make na-montmorillonite through following steps through separating calcium base, the magnesium base montmorillonite of purifying:
A) montmorillonite adds water and stirs together with the sodium salt that is equivalent to the about 5-15% of ore weight, makes the suspension ore pulp of concentration about 10%;
B) under 40~100 ℃ of temperature, the ion-exchange reactions time is no less than six hours, during stir frequently;
C) behind the centrifugal or filtering means dehydration, water cleans 1-2 time;
2) add the mantoquita that copper content is equivalent to ore weight 2-10%, or its water-containing crystal salt, add the ore pulp that water is made concentration about 10% again, stir the back under 40~100 ℃ of temperature, the ion-exchange reactions time is no less than six hours, during stir frequently;
3) behind the centrifugal or filtering means dehydration, clean 1-2 time, and dehydration again;
4) the step 3) gains are cool naturally shines dryly, or dries being lower than under 80 ℃ of temperature, selects for use suitable equipment to be ground to less than 300 orders, obtains water content less than 10% powder, stand-by;
Perhaps: the step 3) gains add maximum 5% dispersant, adding water stirs, make the ore pulp of 10-30%, select for use suitable spray drying device to carry out drying, the spray dryer EAT should be controlled at 150~180 ℃ of scopes, the discharging opening temperature is no more than 70 ℃, obtains water content less than 10% powder, and is stand-by;
Perhaps: step (3) gains add maximum 5% dispersant, add water and stir, and make the suspension of debita spissitudo again, and are stand-by.
3. a kind of copper-loaded montmorillonite according to claim 2 is solid-state with suspension liquid bactericide and preparation method thereof, it is characterized in that said sodium salt is sodium chloride, sodium nitrate, sodium sulphate.
4. a kind of copper-loaded montmorillonite according to claim 2 is solid-state with suspension liquid bactericide and preparation method thereof, it is characterized in that said mantoquita is copper sulphate, copper chloride, copper nitrate.
5. a kind of copper-loaded montmorillonite according to claim 2 is solid-state with suspension liquid bactericide and preparation method thereof, it is characterized in that said dispersant is a sodium tripolyphosphate, tetrasodium pyrophosphate, one or more in the sodium lignosulfonate.
CN 01145558 2001-12-27 2001-12-27 Copper-carried montmorillonite solid and liquid disinfectant and preparation process Pending CN1358441A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 01145558 CN1358441A (en) 2001-12-27 2001-12-27 Copper-carried montmorillonite solid and liquid disinfectant and preparation process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 01145558 CN1358441A (en) 2001-12-27 2001-12-27 Copper-carried montmorillonite solid and liquid disinfectant and preparation process

Publications (1)

Publication Number Publication Date
CN1358441A true CN1358441A (en) 2002-07-17

Family

ID=4678233

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 01145558 Pending CN1358441A (en) 2001-12-27 2001-12-27 Copper-carried montmorillonite solid and liquid disinfectant and preparation process

Country Status (1)

Country Link
CN (1) CN1358441A (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003077674A1 (en) * 2002-03-18 2003-09-25 Zhejiang University A feed additive of nanometer size, a process preparing the same and a feed containing the feed additive of nanometer size
CN100364406C (en) * 2006-01-16 2008-01-30 宁夏大学 Ion-oxide type/organic montmorillonite germicide and its preparing method
CN100364409C (en) * 2006-04-07 2008-01-30 浙江大学 Preparation method and purpose of copper-carried silicate antimicrobial agent
CN100381055C (en) * 2006-04-07 2008-04-16 浙江大学 Preparation method and purpose of zinc-carried silicate antimicrobial agent
CN102578150A (en) * 2012-02-08 2012-07-18 福建师范大学 Method for preparing tea saponin/copper compound antibacterial agent
CN105454293A (en) * 2016-01-11 2016-04-06 济南康众医药科技开发有限公司 Inorganic plant fungicide
CN105519577A (en) * 2016-01-11 2016-04-27 济南康众医药科技开发有限公司 Novel application of Smecta in controlling vegetable diseases
CN105639191A (en) * 2015-12-31 2016-06-08 西南大学 Feed additive for protecting intestinal health of hybrid snakehead fish and preparation method of feed additive
CN108854587A (en) * 2018-06-28 2018-11-23 山东大学 A kind of high-throughput, antibacterial type doping hectorite-metal ion reverse osmosis composite membrane preparation method
WO2021102746A1 (en) * 2019-11-27 2021-06-03 惠州学院 Dry powder paint with long-lasting antibacterial and antifungal effect and preparation method therefor

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003077674A1 (en) * 2002-03-18 2003-09-25 Zhejiang University A feed additive of nanometer size, a process preparing the same and a feed containing the feed additive of nanometer size
CN100364406C (en) * 2006-01-16 2008-01-30 宁夏大学 Ion-oxide type/organic montmorillonite germicide and its preparing method
CN100364409C (en) * 2006-04-07 2008-01-30 浙江大学 Preparation method and purpose of copper-carried silicate antimicrobial agent
CN100381055C (en) * 2006-04-07 2008-04-16 浙江大学 Preparation method and purpose of zinc-carried silicate antimicrobial agent
CN102578150A (en) * 2012-02-08 2012-07-18 福建师范大学 Method for preparing tea saponin/copper compound antibacterial agent
CN102578150B (en) * 2012-02-08 2013-11-20 福建师范大学 Method for preparing tea saponin/copper compound antibacterial agent
CN105639191A (en) * 2015-12-31 2016-06-08 西南大学 Feed additive for protecting intestinal health of hybrid snakehead fish and preparation method of feed additive
CN105454293A (en) * 2016-01-11 2016-04-06 济南康众医药科技开发有限公司 Inorganic plant fungicide
CN105519577A (en) * 2016-01-11 2016-04-27 济南康众医药科技开发有限公司 Novel application of Smecta in controlling vegetable diseases
CN108854587A (en) * 2018-06-28 2018-11-23 山东大学 A kind of high-throughput, antibacterial type doping hectorite-metal ion reverse osmosis composite membrane preparation method
CN108854587B (en) * 2018-06-28 2021-05-25 山东大学 Preparation method of high-flux antibacterial doped hectorite-metal ion reverse osmosis composite membrane
WO2021102746A1 (en) * 2019-11-27 2021-06-03 惠州学院 Dry powder paint with long-lasting antibacterial and antifungal effect and preparation method therefor

Similar Documents

Publication Publication Date Title
CN101696136B (en) Passivating agent for reducing bioavailability of heavy metals in livestock waste compost and using method thereof
US20140065306A1 (en) Nanostructured calcium-silver phosphate composite powders, process for obtaining the powders and bactericidal and fungicidal applications thereof
RU2407289C1 (en) Nanostructured biocide composition
DE102007020242A1 (en) Biocatalysts, processes for their preparation and their use
CN1358441A (en) Copper-carried montmorillonite solid and liquid disinfectant and preparation process
CN1188039C (en) Light-stable inorganic powder silver-carried long-effective anti-bacterial powder and its preparation method
CN111067917A (en) Composite material loaded with nano zinc oxide and preparation method thereof
CN101050365A (en) Modifying agent for bottom material of pond for breeding aquatic products
Ma et al. Antibacterial Activity of Cu 2+-ZnO-modified 13X Zeolite against E. coli and S. aureus
CN1201661C (en) Copper-bearing sepiolite, palygorskite solid and suspension liquid fungicide and its preparation method
CN108033509B (en) Biomass water body multistage water treatment agent
CN101746865A (en) Purifying material, preparation method thereof and method utilizing purifying material to purify water
CN1283154C (en) Stilbite carrier zine series inorganic germicide
KR100949719B1 (en) Antibacterial zeolite resin composition
CN108530655A (en) A kind of antibacterial plastic concentrate and preparation method for antibiotic plastic
CN106467439A (en) A kind of drainage scheme for planting healthy agricultural product
CN100502659C (en) Copper-carried rectorite bactericide and preparation method thereof
JP2969316B2 (en) Sterilization materials using metal ions and zeolite compounds
Zuo et al. Synergistic promotion system of montmorillonite with Cu2+ and benzalkonium chloride for efficient and broad-spectrum antibacterial activity
CN1151718C (en) Animal and fowl disinfectant using nano material as carrier and preparation method thereof
CN1230078C (en) High temp. resistant, colour fastness inorganic antimicrobial mildew preventive agent and its preparing method
CN1162336C (en) Efficient nano water improver and its preparing process
CN114532364B (en) Method for preparing nano-selenium/attapulgite composite antibacterial material by using olive leaf extract
CN118104645B (en) Preparation method of hectorite with antibacterial property
KR0178333B1 (en) Bacillus bacterium and bactericide and preparation method thereof

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication