CN104743681B - The preparation method and application of sewage purification medium - Google Patents
The preparation method and application of sewage purification medium Download PDFInfo
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- CN104743681B CN104743681B CN201510173163.4A CN201510173163A CN104743681B CN 104743681 B CN104743681 B CN 104743681B CN 201510173163 A CN201510173163 A CN 201510173163A CN 104743681 B CN104743681 B CN 104743681B
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Abstract
The invention discloses the preparation method and application of sewage purification medium, initiator is obtained using polymer microsphere and 2 bromo isobutyl acylbromides under 4 dimethylamino naphthyridines are catalyzed, cuprous bromide, 22 bipyridyls and poly- 6 glycolmethacrylates are added to react the polymer microsphere that must activate, polymer microsphere and carbonyl dimidazoles and 4 dimethylamino naphthyridines are reacted the polymer brush obtaining activating and are reacted with bactericidal action protein and 4 dimethylamino naphthyridine lucifuges, obtain final product sewage purification medium.The method preparation process is simple, the sewage purification medium of preparation has good hydrophilic using after polymer microsphere surface modification, sewage surface can be suspended in, good with the contact of sewage, be conducive to lysozyme for carrier protein to the absorption of heavy metal in sewage and sterilizing, immiscible with water it is easy to itself and sewage are separated, postmenstruation process after repeatable utilize.
Description
Technical field
The present invention relates to the dirty water decontamination handles field, the specially preparation method and application of sewage purification medium.
Background technology
Hospital sewage source and complicated component, in addition to there is poisonous, harmful physical chemistry pollutant and radioactive pollution,
Also contain the pathogenic microbes such as antibacterial, virus, there is the features such as space-pollution, acute infection and latent infection, if not
Through effective process, not only pollute the environment, and the important channel of epidemic disease diffusion can be become.China's state environment protecting standard
(HJ2029-2013) in, strictly regulate Hospital Sewage Treatment engineering technology, indicate the height for Hospital Sewage Treatment for the country
Degree is paid attention to.
The method commonly used currently for Hospital Sewage Treatment includes physical method, chemical method and biological method.Physics
Method is mainly disinfection by ultraviolet light, and the method unharmful substance is remaining, and easy and simple to handle, cost is relatively low, but will to the water quality processing
Ask higher and no follow-up bactericidal action.Chemical method mainly includes chlorination method, ozone disinfection, electrochemical process and photocatalyst skill
Art, although wherein first two method disinfection effect is good, has toxicity in itself to disinfectant, such as deals with improperly, have
Certain risk simultaneously causes secondary pollution；Before using electrochemical disinfection, need sewage is carried out with two stage treatment and biology is lived
Property carbon filter, sewage sample be there are certain requirements；Although photocatalyst technology has sterilizing and removes the nuisances such as removing heavy metals
The dual-use function of matter, but its restrictive factor is more and is not also widely used.Biological method is divided into one according to processing intensity
Level processes (physical treatment), two stage treatment (biological treatment) and simple biochemical treatment, and the technique that it adopts has methanepurifying pool
Simple biochemical treatment, activated sludge process, biological contact oxidation process, Gas biological filter and biofilm reactor method etc., in fact
Matter is using the Organic substance in microbial degradation hospital sewage, eliminates the basis that pathogenic microorganism is depended on for existence, but can not
The harmful substances such as heavy metal are removed.Based on the deficiency of above sewage water treatment method, it is contemplated that preparing a kind of pair of work(
The biological affine filler of sewage purification of the high anti-soil of energy, this filler not only has functions that sterilizing, also adsorbable hospital sewage
In heavy metal ion.Bactericidal action protein including thermolysin, lysozyme, sterilization permeability- increasing protein,
Lactoferrin.Do simple introduction below taking lysozyme as a example.
Lysozyme (lysozyme) is also known as muramidase (muramidase) or N-acetylmuramide lycanohydrlase (N-
Acetylmuramide glycanohydrlase), it is a kind of alkaline enzyme that can hydrolyze mucopolysaccharide in pathogenic bacterium.Mainly pass through broken
β between -acetylmuramic acid in bad cell wall and NAG-Isosorbide-5-Nitrae glycosidic bond, makes cell wall insoluble glutinous many
Sugar decomposition becomes solubility glycopeptide, leads to the effusion of cell wall rupture content to make bacterolysises.Lysozyme also can with negatively charged
Virus protein directly in conjunction with, with DNA, RNA, apoprotein formed double salt, make virally inactivated.Therefore, this enzyme have antibacterial,
Antiinflammatory, antiviral etc. act on.Lysozyme can stable existence in acid medium；There are some researches prove, at 96 DEG C, pH value is 3 conditions
Under, after 15min, the vigor of lysozyme can also keep 87%, high temperature and severe sour environment is described to its activity influence less,
The sterilizing that can be used for sewage is processed.
Technique for gene engineering is widely used in terms of the acquisition of numerous protein, isolates and purifies it will usually in mesh for convenience
The N-terminal of albumen, C-terminal or its two ends add polyhistidine label.Imidazole radicals are contained, imidazole ring can be with weight in histidine
There is chelation with coordinate bond in metal ion (such as lead ion, chromium ion, nickel ion, copper ion and cadmium ion etc.), thus having
There iss adsorbable heavy metal, if being used for sewage disposal, the heavy metal in sewage can be removed by it.And for absorption
The lysozyme sewage purification medium of heavy metal, when reclaiming and remove heavy metal, the imidazoles of available high concentration is by heavy metal eluting
Get off, this medium can also reuse again.Traditional hospital sewage purification medium mostly only has sterilizing or absorption
One of two kinds of functions of heavy metal ion, the recycling degree of sewage purification medium is not high, can produce the by-products such as mud.
Content of the invention
It is an object of the invention to provide the preparation method and application of sewage purification medium, preparation method is simple to operation,
This sewage purification medium has the dual-use function of sterilizing, Adsorption of Heavy Metals, and this sewage purification medium will not produce toxic
The by-product of effect, repeatable utilization after simple process.
For achieving the above object, the present invention adopts the following technical scheme that：
The preparation method of sewage purification medium, comprises the following steps：
(1), the polymer microsphere of the surface modification being suspended in aqueous solution and DMAP are dissolved in drying
In dichloromethane, it is sufficiently stirred for rear Deca trifluoroacetic acid and the mixed liquor of 2- bromo isobutyl acylbromide, under condition of ice bath, continue stirring 2
Hour, then reaction temperature is warmed to room temperature continuation stirring 12 hours；
(2) put into after, being washed successively with dry dichloromethane, acetone and methanol after the completion of step (1) solution reaction
60 DEG C of dryings 12 hours in vacuum drying oven；
(3), step (2) is dried the polymer microsphere addition that gained can be suspended in the surface modification in aqueous solution 12 hours
In solution after mixing degassing containing glycolmethacrylate, 2-2 bipyridyl and solvent, add catalyst, 60 DEG C of nitrogen
Gas shielded stirring reaction stops surface transition free radical polymerization reaction, gained after being washed successively with pure water and methanol after 3 hours
The polymer microsphere nitrogen of the surface modification being suspended in aqueous solution dries up；
(4), by step (3) the polymer microsphere of surface modification in the be suspended in aqueous solution that dries up of handy nitrogen add
Enter in the dimethyl sulfoxide containing carbonyl dimidazoles and DMAP, reaction 6 is stirred at room temperature under nitrogen protection little
When, reaction gained can be suspended in polymer microsphere dimethyl sulfoxide, water and the phosphate-buffered of the surface modification in aqueous solution
Liquid washs successively；
(5), the phosphate buffer containing bactericidal action protein is added being suspended in carbonyl dimidazoles activation
In the polymer microsphere of the surface modification in aqueous solution, room temperature reaction 2 hours, obtain final product this sewage purification medium.
The solvent of described step (3) is the mixed liquor of first alcohol and water, and methanol and water volume ratio are 4：1.
Described step (4) bactericidal action protein is thermolysin, lysozyme, sterilization permeability- increasing protein, breast
Any one of ferritin.
The polymer microsphere of the described surface modification being suspended in aqueous solution is amino microsphere, carboxyl microsphere, polyphenyl second
Micro- any one of alkene microsphere, polyvinyl alcohol microparticles, polymethyl methacrylate.
The catalyst of described step (3) is CuBr and CuBr2.
Present invention also offers the sewage purification medium that the preparation method of sewage purification medium is obtained,
This sewage purification medium is used for the process of hospital sewage, the sewage containing pathogenic microorganism, virus and heavy metal
Process.
Beneficial effects of the present invention are：The preparation method of sewage purification medium, its preparation process is simple to operation, preparation
Sewage purification medium uses the polymer microsphere of the surface modification being suspended in aqueous solution, has after surface modification
Hydrophilic, can be suspended in sewage surface well, good with the contact of sewage, be conducive to lysozyme for carrier protein to dirt
The absorption of heavy metal and sterilizing in water；The sewage purification medium being prepared and water immiscible it is easy to by itself and sewage
Separate, repeatable utilization after postmenstruation process；Easy and simple to handle during process sewage, and do not produce other harmful side products.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated.
(1), 1g amino microsphere and 0.08g DMAP (DMAP) are dissolved in 30mL dry methylene chloride, fill
Divide the mixed liquor of Deca 1.25mL trifluoroacetic acid and 8mmol 2- bromo isobutyl acylbromide after stirring, under condition of ice bath, continue stirring 2
Hour, then reaction temperature is warmed to room temperature continuation stirring 12 hours；
(2) put into after, being washed successively with dry dichloromethane, acetone and methanol after the completion of step (1) solution reaction
60 DEG C of dryings 12 hours in vacuum drying oven；
(3), by step (2) be dried 12 hours gained amino microspheres add containing glycolmethacrylate (17.5mL,
63mmol), the mixed liquor (V of 2-2 bipyridyl (490mg, 3.15mmol) and first alcohol and waterWater：VMethanol=1:4) after mixing degassing
Solution in, add CuBr (180mg, 1.26mmol) and CuBr2(14mg, 0.063mmol), 60 DEG C of nitrogen protect stirring reaction
Stop surface transition free radical polymerization reaction, the amino microsphere nitrogen of gained after being washed successively with pure water and methanol after 3 hours
Dry up；
(4), by step (3) the amino microsphere that dries up of handy nitrogen be added to containing carbonyl dimidazoles (0.32g) and 4-
In the 50mL dimethyl sulfoxide (DMSO) of dimethylamino naphthyridine (0.24g), reaction 6 hour is stirred at room temperature under nitrogen protection, instead
Gained amino microsphere dimethyl sulfoxide, water and phosphate buffer is answered to wash successively；
(5), the phosphate buffer containing lysozyme (LZM) is added to the amino microsphere of carbonyl dimidazoles activation,
Room temperature reaction 2 hours, obtains final product this sewage purification medium.
It is below the synthetic route of the preparation method of sewage purification medium of the present invention：
This sewage purification medium is applied in processing hospital sewage, takes hospital sewage 1L, wherein contains coliform and weight
Metal ion, including lead ion (Pb2+), chromium ion (Cr2+), nickel ion (Ni2+), copper ion (Cu2+) and cadmium ion (Cd2 +).The sewage purification preparing medium 1.0g is added to above-mentioned 1L hospital sewage, after being sufficiently stirred for mixing, reacts 2 hours.
Above-mentioned combined sewage is filtered, reclaims sewage purification medium, filtrate is the sewage after processing.Using atomic absorption spectrography (AAS) and many
Pipe fermentation method detects heavy metal in sewage and the content of excrement colibacillus group respectively.Table 1 is the sewage using preparation in the present invention
Before and after purification medium processes sewage, the situation of change of excrement colibacillus group and content of beary metal in sewage.
Table 1 is to pollute using in hospital sewage before and after the lysozyme difunctional sewage purification media processes based on polymer brush
The maximum emission standard of the content of thing, clearance rate and national regulation
As can be seen from the table, after this difunctional media processes sewage, the excrement colibacillus group in sewage and heavy metal
Ion all reaches the hospital wastewater discharge standard (GBJ48-83) of national regulation, and the clearance rate of wherein excrement colibacillus group is
98.21%, heavy metal Pb2+,Cr2+,Ni2+,Cu2+And Cd2+Clearance rate be respectively 80.19%, 67.46%, 85.57%,
79.18% and 95.77%.
Claims (7)
1. the preparation method of sewage purification medium is it is characterised in that comprise the following steps：
(1), the polymer microsphere of the surface modification being suspended in aqueous solution and DMAP are dissolved in and dichloro is dried
In methane, it is sufficiently stirred for rear Deca trifluoroacetic acid and the mixed liquor of 2- bromo isobutyl acylbromide, continue stirring 2 under condition of ice bath little
When, then reaction temperature is warmed to room temperature continuation stirring 12 hours；
(2) put into vacuum after, being washed successively with dry dichloromethane, acetone and methanol after the completion of step (1) solution reaction
60 DEG C of dryings 12 hours in drying baker；
(3), the polymer microsphere that step (2) is dried the surface modification that 12 hours gained can be suspended in aqueous solution adds and contains
In solution after the mixing degassing of glycolmethacrylate, 2-2 bipyridyl and solvent, add catalyst, 60 DEG C of nitrogen are protected
Shield stirring reaction stopped surface transition free radical polymerization reaction after 3 hours, and after being washed successively with pure water and methanol, gained hangs
The polymer microsphere nitrogen floating on the surface modification in aqueous solution dries up；
(4), by step (3) the polymer microsphere of surface modification in the be suspended in aqueous solution that dries up of handy nitrogen be added to
In dimethyl sulfoxide containing carbonyl dimidazoles and DMAP, reaction 6 hour is stirred at room temperature under nitrogen protection, instead
Answer gained can be suspended in polymer microsphere dimethyl sulfoxide, water and the phosphate buffer of the surface modification in aqueous solution successively
Washing；
(5), by the phosphate buffer containing bactericidal action protein add to carbonyl dimidazoles activation be suspended in water-soluble
In the polymer microsphere of the surface modification in liquid, room temperature reaction 2 hours, obtain final product this sewage purification medium.
2. the preparation method of sewage purification medium as claimed in claim 1 is it is characterised in that the solvent of described step (3) is
The mixed liquor of first alcohol and water, and methanol and water volume ratio are 4：1.
3. the preparation method of sewage purification medium as claimed in claim 1 is it is characterised in that described step (5) bactericidal action
Protein be thermolysin, lysozyme, sterilization permeability- increasing protein, lactoferrin any one.
4. the preparation method of sewage purification medium as claimed in claim 1 is it is characterised in that described be suspended in aqueous solution
Surface modification polymer microsphere be amino microsphere, carboxyl microsphere, polystyrene microsphere, polyvinyl alcohol microparticles, poly- methyl-prop
Any one of e pioic acid methyl ester microsphere.
5. the preparation method of sewage purification medium as claimed in claim 1 is it is characterised in that the catalyst of described step (3)
For CuBr and CuBr2.
6. the sewage purification medium being obtained by the preparation method of the arbitrary described sewage purification medium of claim 1-5.
7. the sewage purification medium being obtained by the preparation method of the arbitrary described sewage purification medium of claim 1-5, its feature
It is, this sewage purification medium is used for the process of hospital sewage, at the sewage containing pathogenic microorganism, virus and heavy metal
Reason.
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| CN103127918B (en) * | 2011-09-23 | 2014-09-10 | 重庆文理学院 | Preparation method of drinking water treatment agent |
| CN102617772B (en) * | 2012-04-01 | 2013-10-30 | 无锡格瑞恩环保科技有限公司 | Method for preparing polystyrene microspheres for heavy metal ion water treatment |
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