A kind of preparation method of the bactericidal nano-silver agent for recirculated cooling water
Technical field
The present invention relates to circulating water cooling treatment medicament, be specifically related to a kind ofly effectively to kill bacterium in recirculating cooling water system and the bactericide of environmental protection.
Background technology
In industrial circulating cooling water and oil field reinjection water system, there is a large amount of various microorganism (algae, bacterium, fungi etc.), silt, incrustation scale, dust and microbial death body in various microorganism and secretion thereof and water body together form biological clay.Biological sludge in industrial and harmful microorganism secretion thing acting in conjunction, cause hardware underdeposit corrosion and damage, thus shorten the service life of equipment, reduce the heat exchange effect of heat exchanger, have a strong impact on production.In oilfield exploitation, these bacteriums and microorganism not only can cause corrosion and the pipeline blockage of drilling and ground profit treatment facility, also can destroy oil reservoir and pore permeability be declined, greatly reduces the harm such as water flood recovery efficiency.These are run all to industry and field produces and bring huge economic loss.Therefore, effectively must suppress microorganisms such as the bacterium algaes in various water treatment system.
The sterilizing effective and economic as most convenient and biological clay suppress means, add bactericide and widely applied by each water treatment user in the whole world always in water system.Desirable bactericide requires to have that sterilization is efficient, sludge stripping is effective, drug resistance is good, compatibility is good simultaneously, acid and alkali-resistance, resisting high temperature, high salt, environmental friendliness and many performances such as with low cost, existing bactericide kind is a lot of in the market, but each Properties of Bactericides all can not accomplish to possess the performance that aforementioned desirable bactericide possesses simultaneously.In the exploitation of new bactericide, people are general or pursuit has especially significantly characteristic in a certain respect, or allow new bactericide have the feature of desirable bactericide as much as possible.
Nano Silver is a class antibacterial agent, and have the antibacterial activity of powerful antibacterial, bactericidal action and wide spectrum thereof, have the antibacterial effect that conventional inorganic antibacterial agent is incomparable, have no drug resistance, safety is high.Along with antibiotic bacterial drug resistance is day by day serious, Nano Silver is more and more subject to extensive concern at the investigation and application in disinfection field.
Shitosan also has bactericidal action, and in acid condition, the amino in chitosan molecule, with positive charge, adsorbs the bacterium with negative electrical charge, makes the negative electrical charge skewness on bacteria cell wall and cell membrane, and interference cell wall synthesizes, and causes bacterial death.
Prior art, directly adds to nano silver particles in washing agent, to prepare the washing agent with antibiotic property.But this technology has following deficiency: 1, Nano Silver is stable not in water, easily reunites; 2, Nano Silver disperses even not in water.Though the silica supports anti-biotic material adopting silica to prepare Nano Silver as carrier is had existing, but inapplicable in recirculated cooling water, the preparation scheme of bactericidal nano-silver agent is prepared in order to overcome above-mentioned technical problem.
Summary of the invention
The object of the invention is to overcome the above-mentioned problems in the prior art, provide a kind of can the bactericide of effectively sterilization and the various bacterium of antibacterial recirculating cooling water system and biological clay.
The invention discloses a kind of preparation method of the bactericidal nano-silver agent for recirculated cooling water, the method adopts shitosan and shitosan base polymer to be that carrier fixes Nano Silver method, comprises the following steps:
1) be dissolved in hydrotropy acid solution by shitosan and shitosan base polymer, with sodium hydroxide-ethyl acetate solution for coagulation bath, by being titrated to by chitosan solution in sodium hydroxide-ethyl acetate solution, obtained fixation support is chitosan bead;
2) to 1) add glutaraldehyde solution and Span-80 solution in step chitosan bead, chitosan bead is made to carry out crosslinking activation, reaction certain hour, after use deionized water cyclic washing, until without unreacted glutaraldehyde, obtain the fixation support of crosslinking activation, the chitosan bead of crosslinking activation;
3) preparation of bactericidal nano-silver agent solution:
Take the shitosan that percentage by weight is 0.4-0.5%, add the deionized water that percentage by weight is 98-99%, then add the glacial acetic acid that percentage by weight is 0.3-1%, stir and make it dissolve, add polyethylene of dispersing agent pyrrolidones 0.3-1% and stir and obtain solution A;
Take the AgNO that percentage by weight is 0.2-0.5%
3, added in beaker, then adding percentage by weight is in the water of 99.8-99.5%, stirs and makes it dissolve, obtain solution B;
Solution B is slowly added dropwise in solution A, after dropwising, adds and account for the absolute ethyl alcohol that total weight percent is 5-10%, be warming up to 55-65 DEG C, isothermal reaction 6-10h, obtain golden yellow bactericidal nano-silver agent solution; The mass ratio of described solution B and described solution A is 2-3:1;
4) by 2) leaching of step crosslinking activation chitosan bead is placed in 3) the nanometer silver antimicrobial agent solution of step, under 3 DEG C of-7 DEG C of environment, reaction 4h-6h, repeatedly chitosan bead is rinsed after completion of the reaction by deionized water, until be eluted without Nano Silver, obtain through the immobilized bactericidal nano-silver agent of chitosan bead.
In the preparation method stated on the invention, wherein said Nano Silver weight is containing 10mg/l-1000000mg/l, and the particle diameter of Nano Silver is between 1-100nm.
In the preparation method stated on the invention, wherein the hydrotropy acid of shitosan and shitosan base polymer is preferably one or more of nitric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, hydrochloric acid and citric acid.
Further technical scheme is: in step 2) in, the glutaraldehyde solution concentration v/v added in (1) step is 8%, Span-80 concentration v/v is 2%, and crosslinking temperature is 20 DEG C, and crosslinking time is 7h; (4) in step, immobilization temperature is 3-6 DEG C, and the set time is 7-9h.
Shitosan of the present invention is a kind of chitin deacetylase product, has very large advantage in hydrophily, recyclability and biocompatibility.Shitosan is configured to amido glucose substantially, containing abundant amino and hydroxyl, can carry out base group modification, also can be made into spheroidal material for the field such as medicament slow release, immobilization.
Product of the present invention is compared with conventional sterilization agent, there is the feature such as broad-spectrum high efficacy, nontoxic and extremely strong antibacterial action, be applicable to industrial circulating cooling water system, oil field reinjection water and wastewater treatment, there is high kill efficiency to the bacteriums such as common heterotroph (TGB), sulfate reducing bacteria (SRB) and iron bacteria (FB) and algae, to preventing the formation of biological sludge in industrial, there is excellent effect.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of nano-silver antiseptic solution.
Embodiment
Below in conjunction with embodiment, explanation is further explained to the present invention.
The preparation of example 1 bactericidal nano-silver agent
Bactericidal nano-silver agent is preparation method comprise the following steps:
(1) fixation support is prepared: 2.5g shitosan being joined v/v is in 100ml2% acetic acid solution, abundant stirring, be mixed with the chitosan solution that v/v is 2.5%, v/v 8g sodium hydroxide being joined 200ml is in 60% ethyl acetate solution, abundant dissolving, be mixed with sodium hydroxide-ethyl acetate solution that v/v is 4%, the disposable medical 5ml syringe that syringe needle model is 27G is used to draw 3ml chitosan solution, by syringe needle, chitosan solution is titrated in sodium hydroxide-ethyl acetate solution, namely making chitosan bead is fixation support, use deionized water cyclic washing again, until remain without sodium hydroxide, save backup at being positioned over 4 DEG C,
(2) crosslinking activation fixation support: choose fixation support chitosan bead 2g, add 50ml8% glutaraldehyde solution and 2%Span-80 solution, 3h is reacted at 20 DEG C, use deionized water cyclic washing after completion of the reaction, until without unreacted glutaraldehyde, obtain the fixation support chitosan bead of crosslinking activation;
(3) choose immobilized Nano silver solution: be dissolved in 100ml water by 0.4g shitosan, add acetic acid 1ml, stir and make it dissolve.By 0.14gAgNO
3be dissolved in 40ml water, by AgNO
3solution is added drop-wise in chitosan aqueous solution, and then drips 10ml ethanol, and 80 DEG C of reaction 6h, obtain golden yellow Nano silver solution.
(4) Nano Silver immobilization: the leaching of (2) step crosslinking activation chitosan bead is placed in 10ml nano-silver antiseptic solution, under 4 DEG C of environment, reaction 4h, repeatedly chitosan bead is rinsed after completion of the reaction by deionized water, until be eluted without Nano Silver, obtain through the immobilized bactericidal nano-silver agent of chitosan bead.
The evaluation of example 2 bactericidal property
The method of evaluating performance of bactericide adopts, and [the test bottle method of plate count and dilution-to-extinction method, reference standard be the mensuration plate count of mucus formation bacterium " in the industrial circulating cooling water " (GB/T14643.1-2009), the mensuration MPN method of sulfate reducing bacteria " in the industrial circulating cooling water " (GB/T14643.5-2009), the mensuration MPN method of iron bacteria " in the industrial circulating cooling water " (GB/T14643.6-2009) and " Performance Valuation of Bactericides method " (SY/T5890-1993).
Sulfate reducing bacteria (SRB) bacterial classification takes from northeast oil field extracted water, and bacteria suspension adopts this oil field extracted water to prepare, bacterium medicine 2h time of contact, T=45 DEG C; Heterotroph (TGB) and iron bacteria (FB) bacterial classification from chemical plant, Tianjin cycle water, the on-the-spot water preparation of this factory of bacteria suspension, time of contact 4h, T=37 DEG C.
Bactericidal nano-silver agent obtained for the embodiment of the present invention 1 is carried out bactericidal property with other medicaments compare, choose the adding consistency of various medicament according to the basically identical principle of cost.Table 1 is sterilization test result.
The bactericidal property evaluation comparison of table 1 Nano Silver agent of the present invention and other medicaments
Note: in (1) table 1, bactericide used: A is indication Nano Silver agent of the present invention product in embodiment 2; Isothiazolinone, 14% industrial goods; DBNPA, DBNE, BNPD, DBMAL are the industrial goods of purity >=99%;
(2) the blank bacterium number of TGB, SRB, FB is followed successively by: 7.0 × 10
-7individual/mL, 2.5 × 10
-6individual/mL, 2.0 × 10
-5individual/mL.
From table 1 bacterium test result, A has very excellent bactericidal property.