CN108642032A - Embedded immobilization microbial carrier and preparation method thereof and sewage water treatment method - Google Patents
Embedded immobilization microbial carrier and preparation method thereof and sewage water treatment method Download PDFInfo
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- CN108642032A CN108642032A CN201810720513.8A CN201810720513A CN108642032A CN 108642032 A CN108642032 A CN 108642032A CN 201810720513 A CN201810720513 A CN 201810720513A CN 108642032 A CN108642032 A CN 108642032A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/04—Enzymes or microbial cells immobilised on or in an organic carrier entrapped within the carrier, e.g. gel or hollow fibres
Abstract
A kind of embedded immobilization microbial carrier of present invention offer and preparation method thereof and sewage water treatment method.The preparation method of embedded immobilization microbial carrier of the present invention includes：Polyvinyl alcohol and sodium alginate are added to the water, heating makes polyvinyl alcohol fully be dissolved with sodium alginate, obtains the first gel solution, first gel solution is cooled to 20 DEG C 40 DEG C；Bacterium solution and gas generating compounds solution are provided, the gas generating compounds are that the compound that can generate gas is reacted with hydrogen ion；The bacterium solution, the gas generating compounds solution, first gel solution are uniformly mixed, the second gel solution is obtained；Crosslinking agent is provided, the crosslinking agent is the aqueous solution containing calcium chloride and boric acid；Second gel solution is instilled dropwise in the crosslinking agent, embedded immobilization microbial carrier is obtained, the embedded immobilization microbial carrier is the gelled pill with multi-pore structure.
Description
Technical field
The present invention relates to sewage treatment field more particularly to a kind of embedded immobilization microbial carrier and preparation method thereof with
Sewage water treatment method.
Background technology
With the rapid emergence of China's process industry, the industry such as mechanical processing, plating and smelting is carrying out at metal surface
When reason, it is often necessary to be washed to metal surface, generate a large amount of washings, shower waste water.Treatment of Metal Surface waste water is rich in each
Kind organic matter, high phosphorus, high nitrogen and poisonous and harmful heavy metallic.The nitrogen of high-content can not only cause the eutrophication of water body can also be to people
Body health causes heavy losses, therefore, it is most important to carry out denitrogenation processing to such waste water.
It is mainly chemical method, biology that the more extensive method of Treatment of Metal Surface wastewater application is handled outside Current Domestic
Method, biochemical binding assay.Nitrogen in Treatment of Metal Surface waste water exists mostly in the form of nitrate nitrogen, and chemical method can remove well
Poisonous and harmful substance in water and high phosphorus, but cannot achieve to the good removal effect of nitrate nitrogen.Traditional biological denitrificaion due to
Denitrogenation flora growth is slower, is easy to be lost in from system with flow, therefore, it is difficult to maintain higher biology in bioreactor dense
Degree has anti-load impact energy force difference, the low defect of volumetric loading rate to limit its large-scale use.
Invention content
The technology of activated sludge or microbial inoculum is embedded using immobilization technology can overcome the shortcomings of traditional denitrogenation.Embedding is fixed
Change technology can targetedly be fixed effective flora, can optionally improve sludge age, keep the activity of efficient bacterium,
Treatment effeciency is greatly improved, processing cost is reduced.
The purpose of the present invention is to provide a kind of preparation method of embedded immobilization microbial carrier, embedding obtained is fixed
Changing microbe carrier has multi-pore structure, to enhance the mass transfer ability of embedded immobilization microbial carrier.
The present invention also aims to provide a kind of embedded immobilization microbial carrier, there is stronger mass transfer ability.
The present invention also aims to provide a kind of sewage water treatment method, the removal efficiency of nitrogenous compound is high, and dirty
Water treatment efficiency is very high.
In order to achieve the above object, present invention firstly provides a kind of preparation methods of embedded immobilization microbial carrier, including：
Polyvinyl alcohol and sodium alginate are added to the water, heating makes polyvinyl alcohol fully be dissolved with sodium alginate, obtains the
First gel solution is cooled to 20 DEG C -40 DEG C by one gel solution；
Bacterium solution and gas generating compounds solution are provided, the bacterium solution is the aqueous solution containing thalline, and the gas generating compounds are
The compound of gas can be generated by being reacted with hydrogen ion；
The bacterium solution, the gas generating compounds solution, first gel solution are uniformly mixed, it is molten to obtain the second gel
Liquid；
Crosslinking agent is provided, the crosslinking agent is the aqueous solution containing calcium chloride and boric acid；
Second gel solution is instilled dropwise in the crosslinking agent, embedded immobilization microbial carrier is obtained, it is described
Embedded immobilization microbial carrier is the gelled pill with multi-pore structure.
Optionally, in first gel solution, the mass percent of polyvinyl alcohol is 10%-15%, sodium alginate
Mass percent is 1%-3%；
In second gel solution, the mass percent of the thalline is 15%-25%, the matter of the gas generating compounds
Amount percentage is 0.3%-0.9%；
In the crosslinking agent, the mass percent of boric acid is 3%-5%, and the mass percent of calcium chloride is 2%-6%.
Optionally, heating makes the polyvinyl alcohol be with the method that sodium alginate fully dissolves：Polyvinyl alcohol and sea will be added with
The water of mosanom is heated to 100 DEG C -130 DEG C, is kept for 10 minutes to 50 minutes；
It is uniformly mixed the bacterium solution, the gas generating compounds solution, first gel solution by the way of stirring；
Second gel solution is dripped from the ullage of the crosslinking agent using peristaltic pump of the end with outlet tube
It adds in the crosslinking agent；
After second gel solution is instilled in the crosslinking agent, stand 15 hours or more.
Optionally, the gas generating compounds include sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus, carbonic acid ammonia, carbonic acid
It is one or more in hydrogen ammonia.
Preferably, the gas generating compounds are sodium bicarbonate.
Optionally, the preparation method of embedded immobilization microbial carrier of the invention further includes：Buffer solution is provided, it will be described
Embedded immobilization microbial carrier is placed in the buffer solution after immersion, is carried out to the embedded immobilization microbial carrier with water
Cleaning.
Optionally, the embedded immobilization microbial carrier is placed in the buffer solution and is impregnated 30 minutes to 2 hours；
The buffer solution is potassium dihydrogen phosphate, a concentration of 0.03mol/L- of the potassium dihydrogen phosphate
0.07mol/L。
The present invention also provides a kind of embedded immobilization microbial carriers prepared using the above method.
The present invention also provides a kind of sewage water treatment methods, including：Sewage containing nitrogenous compound and above-mentioned embedding are provided
Fixed microorganism carrier, fixed microorganism includes denitrification microorganism in the embedded immobilization microbial carrier, described
The embedded immobilization microbial carrier is added in sewage, using the embedded immobilization microbial carrier in the sewage
Nitrogenous compound is degraded.
Optionally, the temperature of the sewage is 20-40 DEG C；The pH value of the sewage is 7-9；The micro- life of embedded immobilization
The volume ratio of object carrier and the sewage is 10%-30%；Carbon-nitrogen ratio in the sewage is 1-3.
Beneficial effects of the present invention：The preparation method of the embedded immobilization microbial carrier of the present invention utilizes gas generating compounds
Solution generates gas with the acid reaction in crosslinking agent, and embedded immobilization microbial carrier obtained is made to have multi-pore structure,
To enhance the mass transfer ability of embedded immobilization microbial carrier.The embedded immobilization microbial carrier of the present invention has concrete dynamic modulus
Structure, thus there is stronger mass transfer ability.The sewage water treatment method of the present invention uses the above-mentioned embedding with multi-pore structure
Fixed microorganism carrier degrades to the nitrogenous compound in sewage, since embedded immobilization microbial carrier has relatively by force
Mass transfer ability, therefore the removal efficiency of nitrogenous compound is high, and sewage treating efficiency is very high.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of the scope of the invention.
Fig. 1 is the flow chart of the preparation method of the embedded immobilization microbial carrier of the present invention.
The mass-transfer performance of embedded immobilization microbial carrier produced by the present invention compares when Fig. 2 is sodium bicarbonate concentration difference
Figure；
Fig. 3 is for embedded immobilization microbial carrier of the invention to Treatment of Metal Surface waste water under the conditions of different carbon-nitrogen ratios
Nitrate nitrogen remove situation；
Fig. 4 is for embedded immobilization microbial carrier of the invention to Treatment of Metal Surface waste water under the conditions of different carbon-nitrogen ratios
Ammonia nitrogen removal situation；
Fig. 5 is for embedded immobilization microbial carrier of the invention to Treatment of Metal Surface waste water under the conditions of different carbon-nitrogen ratios
Nitrite nitrogen remove situation；
Fig. 6 is for embedded immobilization microbial carrier of the invention to Treatment of Metal Surface waste water under the conditions of different carbon-nitrogen ratios
Total nitrogen remove situation；
Fig. 7 is for embedded immobilization microbial carrier of the invention to Treatment of Metal Surface waste water under the conditions of different carbon-nitrogen ratios
COD remove situation；
Fig. 8 is for embedded immobilization microbial carrier of the invention to Treatment of Metal Surface waste water under the conditions of different filling rates
Nitrate nitrogen remove situation；
Fig. 9 is for embedded immobilization microbial carrier of the invention to Treatment of Metal Surface waste water under the conditions of different filling rates
Ammonia nitrogen removal situation；
Figure 10 is that the embedded immobilization microbial carrier of the present invention is useless to Treatment of Metal Surface under the conditions of different filling rates
The nitrite nitrogen of water removes situation；
Figure 11 is that the embedded immobilization microbial carrier of the present invention is useless to Treatment of Metal Surface under the conditions of different filling rates
The total nitrogen of water removes situation；
Figure 12 is that the embedded immobilization microbial carrier of the present invention is useless to Treatment of Metal Surface under the conditions of different filling rates
The COD of water removes situation.
Specific implementation mode
Term as used herein：
" by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing "
Or its any other deformation, it is intended that cover non-exclusionism includes.For example, composition, step, method comprising listed elements,
Product or device are not necessarily limited to those elements, but may include not expressly listed other elements or such composition, step
Suddenly, method, product or the intrinsic element of device.
Conjunction " by ... form " exclude any element that do not point out, step or component.If in claim,
This phrase will make claim be closed, so that it is not included the material in addition to the material of those descriptions, but relative
Except customary impurities.When phrase " by ... form " be rather than immediately following theme in the clause that appears in claim main body after
When, only it is limited to the element described in the clause；Other elements be not excluded the claim as a whole it
Outside.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this, which should be understood as, specifically discloses by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1~5 ", described range should be interpreted as including range " 1~4 ", " 1~3 ", " 1~2 ", " 1~2 and 4~
5 ", " 1~3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise range intention includes its end
Value and all integers and score in the range.
" mass parts " refer to the basic measurement unit for the mass ratio relationship for indicating multiple components, and 1 part can indicate arbitrary list
Position quality, can such as be expressed as 1g, may also indicate that 2.689g etc..If we say that the mass parts of component A are a parts, the matter of B component
It is b parts to measure part, then it represents that the quality of component A and the mass ratio a of B component：b.Alternatively, indicating that the quality of component A is aK, B groups
The quality divided is bK (K is arbitrary number, indicates multiplying factor).It can not misread, unlike mass fraction, all components
The sum of mass parts be not limited to 100 parts of limitation.
"and/or" is used to indicate that one of illustrated situation or both may to occur, for example, A and/or B includes (A
And B) and (A or B)；
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the apparent purport of the quantity refers to singulative.
Referring to Fig. 1, present invention firstly provides a kind of preparation methods of embedded immobilization microbial carrier, including walk as follows
Suddenly：
Polyvinyl alcohol (PVA) and sodium alginate (SA) are added to the water by step 1, and heating makes polyvinyl alcohol and sodium alginate
Fully dissolving, obtains the first gel solution, first gel solution is cooled to 20 DEG C -40 DEG C.
Specifically, in first gel solution, the mass percent of polyvinyl alcohol is 10%-15%, sodium alginate
Mass percent is 1%-3%.
Preferably, in the step 1, the water is deionized water.
Preferably, in the step 1, first gel solution is cooled to 30 DEG C.
Specifically, the polyvinyl alcohol refers to the polyvinyl alcohol that the degree of polymerization is 1750 ± 100, alcoholysis degree ＞ 98%.
Specifically, in the step 1, heating makes the polyvinyl alcohol be with the method that sodium alginate fully dissolves：It will be added with
The water of polyvinyl alcohol and sodium alginate is heated to 100 DEG C -130 DEG C (preferably 121 DEG C), keep 10 minutes to 50 minutes (preferably
It it is 30 minutes).
Step 2 provides bacterium solution and gas generating compounds solution, and the bacterium solution is the aqueous solution containing thalline, the aerogenesis
It is that the compound that can generate gas is reacted with hydrogen ion to close object；
The bacterium solution, the gas generating compounds solution, first gel solution are uniformly mixed, it is molten to obtain the second gel
Liquid.
Specifically, the embedded immobilization microbial that ought subsequently prepare is for removing the nitrogenous compound in sewage
When, contain denitrification microorganism in the bacterium solution.
Optionally, the step 2 makes the bacterium solution, the gas generating compounds solution, described first by the way of stirring
Gel solution is uniformly mixed, speed of agitator 50-80rpm.
Specifically, the preparation method of the bacterium solution is：Thalline culture is provided, by the thalline culture 3000rad/
After min centrifugations, supernatant is outwelled, bottom thalline is taken to be resuspended to obtain bacterium solution with distilled water.
In one embodiment of this invention, the thalline culture is from Lang Kun groups of Shenzhen sewage treatment plant A/A/
The ponds O treatment process A export the activated sludge taken out, contain abundant denitrification microorganism in the activated sludge.
Specifically, in second gel solution, the mass percent of the thalline is 15%-25%, the aerogenesis
The mass percent for closing object is 0.3%-0.9%.
Optionally, the gas generating compounds include sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus, carbonic acid ammonia, carbonic acid
It is one or more in hydrogen ammonia.
Preferably, the gas generating compounds are sodium bicarbonate (FA), this is because the cost of sodium bicarbonate is relatively low, source is wide
General, gas deliverability is strong.
Step 3 provides crosslinking agent, and the crosslinking agent is the aqueous solution containing calcium chloride and boric acid；By second gel
Solution is instilled dropwise in the crosslinking agent, obtains embedded immobilization microbial carrier, and the embedded immobilization microbial carrier is
Gelled pill with multi-pore structure.
Optionally, in the crosslinking agent, the mass percent of boric acid is 3%-5%, and the mass percent of calcium chloride is
2%-6%.
Preferably, in the crosslinking agent, calcium chloride is in saturation or hypersaturated state with boric acid, this is because handing over
Join in reaction process and during air-generating reaction, calcium chloride is in the state constantly consumed with boric acid.
In the step 3, the polyvinyl alcohol is crosslinked with sodium alginate under the crosslinked action of calcium chloride and boric acid
Polymerisation, forms reticular structure, and the gas generating compounds generate gas (such as sodium bicarbonate and boron reacting with boric acid
Acid reaction generates carbon dioxide gas), the gas can form porous in the inside of the embedded immobilization microbial carrier
Gap structure, to promote the mass-transfer performance of embedded immobilization microbial carrier.
Optionally, the step 3 using peristaltic pump of the end with outlet tube by second gel solution from the friendship
The ullage of connection agent is added dropwise in the crosslinking agent.
Optionally, a diameter of 1mm-10mm (such as 5mm) of the end nozzle of the outlet tube, second gel solution
It is added dropwise in the crosslinking agent from away from crosslinking agent liquid level 10cm-20cm (such as 15cm) height.
It is understood that according to the particle size for the embedded immobilization microbial carrier finally wanted to determine
The diameter for stating the end nozzle of peristaltic pump determines second gel solution according to the thickness of the liquid layer of the crosslinking agent
The position height dripped, for example, the crosslinking agent liquid layer it is relatively thin when, second gel solution cannot be made from too high position
Drippage.
Specifically, in the step 3, after second gel solution is instilled in the crosslinking agent, stand 15 hours with
Upper (preferably 15 hours to 25 hours) make cross-linking reaction carry out thorough.
Step 4 provides buffer solution, the embedded immobilization microbial carrier is placed in the buffer solution after impregnating, is used
Water cleans the embedded immobilization microbial carrier repeatedly.
The effect of the step 4 be to remove the embedded immobilization microbial carrier surface and internal residual it is various not
The compound of reaction.
Preferably, in the step 4, the embedded immobilization microbial carrier is placed in the buffer solution and impregnates 30 points
Clock was to 2 hours.
Optionally, the buffer solution is potassium dihydrogen phosphate, pH value 7 or so, the potassium dihydrogen phosphate it is dense
Degree is 0.03mol/L-0.07mol/L.
Can be tap water to the water of the embedded immobilization microbial carrier cleaning specifically, in the step 4.
Specifically, the grain size of the embedded immobilization microbial carrier is 1mm-10mm (such as 5mm).
The preparation method of above-mentioned embedded immobilization microbial carrier utilizes gas generating compounds solution and the boric acid in crosslinking agent
Reaction generates gas, and embedded immobilization microbial carrier obtained is made to have multi-pore structure, micro- to enhance embedded immobilization
The mass transfer ability of bio-carrier, the mass transfer ability include the ability that environmental liquids pass in and out the embedded immobilization microbial carrier
And the ability that the metabolite of the microorganism of the embedded immobilization microbial carrier inside discharges, such as the micro- life of denitrogenation
Object will produce nitrogenous gas when degrading to the nitrate nitrogen in sewage, if these nitrogenous gas cannot be timely from the packet
It buries in fixed microorganism carrier and is discharged, will be accumulated in the embedded immobilization microbial carrier, eventually lead to the packet
Fixed microorganism carrier explosion is buried, it is using the present invention since nitrate nitrogen content is very high in Treatment of Metal Surface waste water
Embedded immobilization microbial carrier made from the preparation method of embedded immobilization microbial carrier is particularly suitable for metal surface
Nitrogenous compound in processing waste water is degraded.
Based on the preparation method of above-mentioned embedded immobilization microbial carrier, above method system is used the present invention also provides a kind of
Standby embedded immobilization microbial carrier.
It is noted that the embedded immobilization microbial carrier of the present invention is due to multi-pore structure, having
Very strong mass transfer ability, is applicable not only to sewage treatment field, additionally it is possible to for fields such as biofermentations, be particularly suitable for needing
The field that aerogenic bacteria is immobilized.
Based on above-mentioned embedded immobilization microbial carrier, the present invention also provides a kind of sewage water treatment methods, including：Offer contains
There are the sewage of nitrogenous compound and an above-mentioned embedded immobilization microbial carrier, it is fixed in the embedded immobilization microbial carrier
Microorganism includes denitrification microorganism, and the embedded immobilization microbial carrier is added in the sewage, solid using the embedding
Surely change microbe carrier to degrade to the nitrogenous compound in the sewage.
Optionally, the temperature of the sewage is 20-40 DEG C, preferably 30 DEG C.
Optionally, the pH value of the sewage is 7-9, preferably 7.5-8.5, more preferably 7.5.
Optionally, in above-mentioned sewage water treatment method, the volume ratio of the embedded immobilization microbial carrier and the sewage
(i.e. carrier filling rate) is 10%-30%.
Preferably, the volume ratio (i.e. carrier filling rate) of the embedded immobilization microbial carrier and the sewage is
20%, it can realize standard water discharge and cost-effective, while can realize higher nitrogen removal efficiency, specifically refer to following realities
Apply example 3.
Specifically, the nitrogenous compound includes one or more in nitrate nitrogen, nitrite nitrogen, ammonia nitrogen.
Optionally, the sewage includes Treatment of Metal Surface waste water, breeding wastewater, pharmacy waste water, petrochemical wastewater, municipal administration dirt
It is one or more in water, landscape water, food wastewater, soy protein wastewater.
Optionally, the carbon-nitrogen ratio in the sewage is 1-3, to meet the needs of microorganism growth.When the sewage raw water
In carbon source deficiency when, carbon source can be added into the sewage so that the carbon-nitrogen ratio in the sewage reaches suitable ratio.
Optionally, the carbon source includes one or more in methanol, glucose, flour, sodium acetate.
Preferably, the carbon-nitrogen ratio in the sewage is 2, can the cost-effective and higher nitrogen removal efficiency of realization, specifically
Refer to following embodiments 2.
Preferably, the processing time of above-mentioned sewage water treatment method be 15h (hour), specifically refer to following embodiments 2 with
Embodiment 3.
Specifically, when fixed microorganism is anaerobe in the embedded immobilization microbial carrier, the dirt
Water treatment procedure also needs to carry out under anaerobic environment.
Optionally, the sewage is Treatment of Metal Surface waste water, due to generally use nitric acid during Treatment of Metal Surface
Metal surface is cleaned, therefore nitrate nitrogen content is very high in Treatment of Metal Surface waste water, under normal conditions the metal watch
The nitrate of surface treatment waste water is 100-120mg/L.
Preferably, the temperature of the Treatment of Metal Surface waste water be 20-40 DEG C, preferably 30 DEG C, pH value 7-9, preferably
For 7.5-8.5, more preferably 7.5, conditions above is conducive to Bali Ali pseudomonad (Pseudomonas balearica)
FX-1 growth and breedings in Treatment of Metal Surface waste water, to accelerate to the nitrate nitrogen compound in Treatment of Metal Surface waste water
Degradation.
Embodiment 1
The present invention is dense to the gas generating compounds solution that is used in the preparation method step 2 of embedded immobilization microbial carrier
Degree optimizes, the specific steps are：
Step 1), preparation method 4 groups of experiments of progress for above-mentioned embedded immobilization microbial carrier, 4 groups of experiments
The concentration of boric acid is 4% (saturated concentration) in the crosslinking agent of use, the gas generating compounds of step 2 use of 4 groups of experiments
Solution is sodium bicarbonate solution, and difference place is：In the step 2 of 4 groups of experiments, carbonic acid in second gel solution
The concentration of hydrogen sodium is respectively 0%, 0.3%, 0.6%, 0.9%, and 4 groups of experiments respectively obtain 4 kinds of embedded immobilization microbials
Carrier；
Step 2) investigates the mass-transfer performance of embedded immobilization microbial carrier made from above-mentioned four groups of experiments, examines
The method of examining is：
The embedded immobilization microbial carrier for taking 10mL sizes almost the same is put into the methylene for filling mass concentration 2mg/L
In the sampling bottle of blue solution, be placed in shaking table rocked with constant speed 250r/min adsorbed after 3h after solution, in 665nm waves
The absorbance of methylene blue solution after long lower measurement absorption.Since the absorbance of methylene blue solution before absorption is identical, inhale
The absorbance size of attached methylene blue solution just reflects the mass-transfer performance of embedded immobilization microbial carrier, and absorbance is got over
Greatly, illustrate that embedded immobilization microbial carrier absorption pigment is fewer, mass-transfer performance is poorer.
1 sample evaluation table of table
In above-mentioned 4th group of experiment, a concentration of the 0.9% of sodium bicarbonate, methylene after absorption in second gel solution
The absorbance of blue solution is minimum, illustrates that the pigment of embedded immobilization microbial carrier absorption is most, and mass-transfer performance is best, but wraps
It is irregular to bury fixed microorganism carrier balling-up, have sprout, size it is uneven.
1st group of experiment in the 2nd group of experiment, in second gel solution concentration of sodium bicarbonate be respectively 0% with
0.3%, the absorbance of methylene blue solution is larger after absorption, illustrates that the pigment of embedded immobilization microbial carrier absorption is less,
Mass-transfer performance is poor, and the mechanical strength of embedded immobilization microbial carrier and stability are poor.
In 3rd group of experiment, a concentration of the 0.6% of sodium bicarbonate in second gel solution, the extinction of solution after absorption
Degree is smaller, illustrates that the pigment of embedded immobilization microbial carrier absorption is more, mass-transfer performance is preferable, and the micro- life of embedded immobilization
The mechanical strength of object carrier and stability are preferable.
Fig. 2 is the section view after embedded immobilization microbial carrier adsorption methylene blue in the 1st group of experiment to the 4th group of experiment
Figure, from figure 2 it can be seen that the mass-transfer performance of the embedded immobilization microbial carrier of the 4th group of experiment is best, the 3rd group of experiment
The mass-transfer performance of embedded immobilization microbial carrier takes second place, the embedded immobilization microbial carrier of the 1st group of experiment and the 2nd group of experiment
Mass-transfer performance it is worst, this is consistent with the result of the absorbance value in above-mentioned table 1.
In summary it analyzes, from the point of view of the indexs such as mass-transfer performance, mechanical strength, balling-up effect, second gel solution
Middle sodium bicarbonate a concentration of 0.6% when embedded immobilization microbial carrier obtained comprehensive performance it is best.
Embodiment 2
The present invention optimizes the carbon-nitrogen ratio of sewage in sewage water treatment method, is as follows：
The micro- life of embedded immobilization of 20mL is added in step 1), the 100mL test bottles for being respectively 1,2,3,4,5,6 to number
Object carrier, then it is the Treatment of Metal Surface waste water of 126.3mg/L and anhydrous that nitrate is added into each test bottle respectively
Sodium acetate (i.e. carbon source) to total volume be 100mL, the number 1 (control), 2,3,4,5,6 test bottle in carbon-nitrogen ratio distinguish
It is 0,1.0,1.5,2.0,2.5,3.0；
The case where carbon-nitrogen ratio is 0 is the case where not adding carbon source in Treatment of Metal Surface waste water, at this time metal
The amount of carbon source is almost nil in surface treatment waste water.
Measurement bottle in step 1) is placed in shaking table by step 2), at 30 DEG C, 200 revs/min culture, 0h, 5h,
10h, 15h, 20h processing time, point was to nitrate nitrogen, nitrite nitrogen, ammonia nitrogen, total nitrogen and the chemistry in Treatment of Metal Surface waste water
Oxygen demand (Chemical Oxygen Demand, COD) measures and calculation processing, obtains the nitre of Treatment of Metal Surface waste water
The removal rate of state nitrogen, total nitrogen and COD.Concrete outcome refer to table 2, table 3, table 4, table 5, table 6 and Fig. 3, Fig. 4, Fig. 5, Fig. 6,
Fig. 7.
The nitrate nitrogen of the different carbon-nitrogen ratios of table 2 removes situation
As shown in table 2, it is 20% in carrier filling rate, carbon-nitrogen ratio is respectively 0,1.0,1.5,2.0,2.5,3.0 condition
It is lower that the variation of the nitrate nitrogen of 0h, 5h, 10h, 15h, 20h processing time point is investigated respectively, the results showed that, carbon-nitrogen ratio is higher,
Nitrate is lower, and it is bigger that nitrate nitrogen removes rate.When carbon-nitrogen ratio is 0,1.0,1.5, the nitrate nitrogen after handling 15 hours is dense
Degree is respectively：98.7mg/L、33.2mg/L、15.8mg/L.With the extension of time, when processing time is 20 hours, nitrate nitrogen
Continue to be reduced to 90.5mg/L, 22.9mg/L, 9.8mg/L, but change less, illustrates carbon-nitrogen ratio deficiency.When carbon-nitrogen ratio increases to
2.0,2.5,3 when, processing 15 hours after nitrate be respectively：0.6mg/L、0.4mg/L、0.2mg/L.When with processing
Between extension, when processing time is 20 hours, nitrate nitrogen continues to be reduced to 0.5mg/L, 0.3mg/L, 0.1mg/L, but changes not
Greatly.From cost-effective upper consideration, when carbon-nitrogen ratio is 2.0, carbon source concentration is suitable, and processing Best Times are 15h, nitre after handling at this time
State nitrogen removal efficiency reaches 99.48%.The data of above-mentioned table 2 are corresponding with the content of Fig. 3.
The ammonia nitrogen removal situation of the different carbon-nitrogen ratios of table 3
In above-mentioned table 3, carbon source is not added in raw water expression in Treatment of Metal Surface waste water, and also not add embedded immobilization micro-
The case where bio-carrier.
As shown in table 3, it is 20% in carrier filling rate, carbon-nitrogen ratio is respectively 0,1.0,1.5,2.0,2.5,3.0 condition
It is lower that the variation of the ammonia nitrogen of 0h, 5h, 10h, 15h, 20h processing time point is investigated respectively, the results showed that, carbon-nitrogen ratio is higher, ammonia
Nitrogen concentration is lower, and ammonia nitrogen removal rate is bigger.The concentration of ammonia nitrogen is always when optimum carbon nitrogen ratio is 2.0, in entire processing procedure
Handle reduced levels.The data of above-mentioned table 3 are corresponding with the content of Fig. 4.
The nitrite nitrogen of the different carbon-nitrogen ratios of table 4 removes situation
In above-mentioned table 4, carbon source is not added in raw water expression in Treatment of Metal Surface waste water, and also not add embedded immobilization micro-
The case where bio-carrier.
As shown in table 4, it is 20% in carrier filling rate, carbon-nitrogen ratio is respectively 0,1.0,1.5,2.0,2.5,3.0 condition
It is lower that the variation of the nitrite nitrogen of 0h, 5h, 10h, 15h, 20h processing time point is investigated respectively, the results showed that, carbon-nitrogen ratio is got over
Height, nitrite nitrogen concentration is lower, and it is bigger that nitrite nitrogen removes rate.Before processing 15 hours, limited by carrier space, nitrous
State concentration has a certain amount of accumulation, but with the extension of processing time, and nitrite nitrogen continuously decreases.It is 2.0 in optimum carbon nitrogen ratio
When, when processing time is 15h, a concentration of 0.22mg/L of nitrite nitrogen.The data of above-mentioned table 4 are corresponding with the content of Fig. 5.
The total nitrogen of the different carbon-nitrogen ratios of table 5 removes situation
In above-mentioned table 5, carbon source is not added in raw water expression in Treatment of Metal Surface waste water, and also not add embedded immobilization micro-
The case where bio-carrier.
As shown in table 5, it is 20% in carrier filling rate, carbon-nitrogen ratio is respectively 0,1.0,1.5,2.0,2.5,3.0 condition
It is lower that the variation of the total nitrogen of 0h, 5h, 10h, 15h, 20h processing time point is investigated respectively, the results showed that, carbon-nitrogen ratio is higher, always
Nitrogen concentration is lower, and it is bigger that total nitrogen removes rate.When carbon-nitrogen ratio is 0,1.0,1.5, due to carbon-nitrogen ratio deficiency, total nitrogen concentration can not reach
Mark discharge.When carbon-nitrogen ratio increases to 2.0,2.5,3.0, the total nitrogen concentration after handling 10 hours is respectively：9.9mg/L、
9.3mg/L、7.6mg/L.With the extension of time, when processing time is 15 hours, total nitrogen continue to be reduced to 1.3mg/L,
0.6mg/L、0.3mg/L.With the extension of time, when processing time is 20 hours, total nitrogen concentration no longer changes.From cost-effective
Upper consideration, when carbon-nitrogen ratio is 2.0, carbon source concentration is suitable, and when processing time is 15 hours, total nitrogen removal efficiency reaches at this time
98.97%.The data of above-mentioned table 5 are corresponding with the content of Fig. 6.
The COD of the different carbon-nitrogen ratios of table 6 removes situation
As shown in table 6, it is 20% in carrier filling rate, carbon-nitrogen ratio is respectively 0,1.0,1.5,2.0,2.5,3.0 condition
Lower change respectively to the COD of 0h, 5h, 10h, 15h, 20h processing time point is investigated, the results showed that, with the increase of processing time,
Downward trend is presented in COD.Wherein, when carbon-nitrogen ratio is 0,1.0,1.5, due to carbon-nitrogen ratio deficiency, the comparison of COD consumption
Soon.When carbon-nitrogen ratio is 2.0, and processing time is 15 hours, COD 151.8mg/L, less than the COD (209.6mg/ in raw water
L).And carbon-nitrogen ratio increases when being 2.5 and 3.0, since carbon-nitrogen ratio is larger, has a unconsumed carbon source, increases water outlet COD.
The data of above-mentioned table 6 are corresponding with the content of Fig. 7.
When the above nitrogen index and COD handling results show that carbon-nitrogen ratio is selected as 2.0, processing time selects 15h treatment effects most
It is good.
Embodiment 3
Filling rate (carrier filling rate) of the present invention to the embedded immobilization microbial carrier of sewage in sewage water treatment method
It optimizes, steps are as follows：
Step 1), be to number 1,2,3,4,5,6 100mL test bottles in be separately added into 0mL, 10mL, 15mL, 20mL,
The embedded immobilization microbial carrier of 25mL, 30mL, then the gold that nitrate nitrogen is 126.3mg/L is added into each test bottle respectively
It is 100mL that metal surface, which handles waste water and anhydrous sodium acetate (i.e. carbon source) to total volume, the number 1 (control), 2,3,4,5,6
Test bottle in carrier filling rate be respectively 0%, 10%, 15%, 20%, 25%, 30%, the number 1,2,3,4,5,6
Test bottle in carbon-nitrogen ratio be 2.0；
Measurement bottle in step 1) is placed in shaking table by step 2), at 30 DEG C, 200 revs/min culture, in 0h, 5h,
10h, 15h time point to nitrate nitrogen, nitrite nitrogen, ammonia nitrogen, total nitrogen and the COD in Treatment of Metal Surface waste water measure with
Calculation processing obtains the nitrate nitrogen of Treatment of Metal Surface waste water, the removal rate of ammonia nitrogen, nitrite nitrogen, total nitrogen and COD.As a result in detail
It is shown in Table 7, table 8, table 9, table 10, table 11 and Fig. 8, Fig. 9, Figure 10, Figure 11, Figure 12.
The nitrate nitrogen of the different filling rates of table 7 removes situation
As shown in table 7, it is 2 in carbon-nitrogen ratio, filling rate is respectively 0,10%, 15%, 20%, 25%, 30% condition
It is lower that the nitrate nitrogen variation of processing time 0h, 5h, 10h, 15h, 20h are investigated respectively, the results showed that, carbon-nitrogen ratio is higher, nitre
State nitrogen concentration is lower, and it is bigger that nitrate nitrogen removes rate.When filling rate is 0,10%, 15%, the nitrate nitrogen after handling 15 hours is dense
Degree is respectively 140.2mg/L, 33.4mg/L, 18.7mg/L.With the extension of time, when processing time is 20 hours, nitrate nitrogen
Variation is little, illustrates filling rate deficiency.When filling rate increases to 0%, 25%, 30%, the nitrate nitrogen after handling 15 hours is dense
Degree is respectively 5.4mg/L, 5.7mg/L, 5.0mg/L.With the extension of time, when processing time is 20 hours, nitrate nitrogen variation
Less.From standard water discharge and cost-effective upper consideration, filling rate is proper when being 20%, and nitrate nitrogen removal efficiency reaches at this time
To 96.34%.The data of above-mentioned table 7 are corresponding with the content of Fig. 8.
The ammonia nitrogen removal situation of the different filling rates of table 8
As shown in table 8, it is respectively 2 in carbon-nitrogen ratio, filling rate is respectively 0,10%, 15%, 20%, 25%, 30% item
The variation of the ammonia nitrogen of 0h, 5h, 10h, 15h, 20h is investigated respectively under part, the results showed that, ammonia nitrogen in entire processing procedure all
In compared with low state.When filling rate is 20%, the concentration of ammonia nitrogen handles always reduced levels in entire processing procedure.Above-mentioned table
8 data are corresponding with the content of Fig. 9.
The nitrite nitrogen of the different filling rates of table 9 removes situation
As shown in table 9, it is respectively 2 in carbon-nitrogen ratio, filling rate is respectively 0,10%, 15%, 20%, 25%, 30% item
The nitrite nitrogen variation of 0h, 5h, 10h, 15h, 20h are investigated respectively under part, the results showed that, in entire processing procedure,
The concentration of nitrite nitrogen all keeps reduced levels.The data of above-mentioned table 9 are corresponding with the content of Figure 10.
The total nitrogen of the different filling rates of table 10 removes situation
As shown in table 10, it is respectively 2 in carbon-nitrogen ratio, filling rate is respectively 0,10%, 15%, 20%, 25%, 30% item
The total nitrogen variation of 0h, 5h, 10h, 15h, 20h are investigated respectively under part, the results showed that, carbon-nitrogen ratio is higher, and total nitrogen concentration is got over
Low, it is bigger that total nitrogen removes rate.When filling rate is 0,10%, 15%, the nitrate after handling 15 hours is respectively
141.3mg/L、34.4mg/L、20.2mg/L.With the extension of time, when processing time is 20 hours, total nitrogen variation is little, says
Bright filling rate is insufficient.When filling rate increases to 20%, 25%, 30%.Processing 15 hours after nitrate be respectively
6.5mg/L、6.3mg/L、5.8mg/L.With the extension of time, when processing time is 20 hours, total nitrogen variation is little.From water outlet
Up to standard and cost-effective upper consideration, filling rate 20%, processing time are that 15h is proper, and total nitrogen removal efficiency reaches at this time
To 95.65%.The data of above-mentioned table 10 are corresponding with the content of Figure 11.
The COD of the different filling rates of table 11 removes situation
As shown in table 11, it is respectively 2 in carbon-nitrogen ratio, filling rate is respectively 0,10%, 15%, 20%, 25%, 30% item
The total nitrogen variation of 0h, 5h, 10h, 15h, 20h are investigated respectively under part, the results showed that, with the increase of processing time, COD
Downward trend is presented.Wherein, when filling rate is 0,10%, 15%, due to filling rate deficiency, total nitrogen index degradation rate
It is smaller, therefore COD consumption is less.When filling rate is 20%, 25%, 30%, with the extension of processing time, COD is gradual
It reduces, when processing time is 15 hours, respectively 121.9mg/L, 120.4mg/L, 112.9mg/L are below the COD in raw water
(188.2mg/L).With the extension of processing time, COD variations are little.The data of above-mentioned table 11 are corresponding with the content of Figure 12.
The above nitrogen index and COD handling results show that filling rate is selected as 20%, and processing time selects 15h treatment effects most
It is good.
Specifically, the embedded immobilization microbial carrier that above-described embodiment 2 is used with embodiment 3 is above-described embodiment 1
In in the second gel solution sodium bicarbonate a concentration of 0.6% when embedded immobilization microbial carrier obtained.
Since the numberical range of each technological parameter involved in the present invention can not possibly all embody in the above-described embodiments,
As long as but those skilled in the art's envisioned any numerical value fallen into the above-mentioned numberical range completely can implement this
Invention also includes the arbitrary combination of occurrence in several numberical ranges certainly.Herein, for length the considerations of, be omitted to
Go out the embodiment of occurrence in certain one or more numberical range, this disclosure for being not to be construed as technical scheme of the present invention is not filled
Point.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, concrete mode selection of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., fall the protection in the present invention
In range.
Claims (10)
1. a kind of preparation method of embedded immobilization microbial carrier, which is characterized in that including：
Polyvinyl alcohol and sodium alginate are added to the water, heating makes polyvinyl alcohol fully be dissolved with sodium alginate, and it is solidifying to obtain first
First gel solution is cooled to 20 DEG C -40 DEG C by sol solution；
There is provided bacterium solution and gas generating compounds solution, the bacterium solution is the aqueous solution containing thalline, and the gas generating compounds are and hydrogen
Ionic reaction can generate the compound of gas；
The bacterium solution, the gas generating compounds solution, first gel solution are uniformly mixed, the second gel solution is obtained；
Crosslinking agent is provided, the crosslinking agent is the aqueous solution containing calcium chloride and boric acid；
Second gel solution is instilled dropwise in the crosslinking agent, embedded immobilization microbial carrier, the embedding are obtained
Fixed microorganism carrier is the gelled pill with multi-pore structure.
2. the preparation method of embedded immobilization microbial carrier as described in claim 1, which is characterized in that first gel
In solution, the mass percent of polyvinyl alcohol is 10%-15%, and the mass percent of sodium alginate is 1%-3%；
In second gel solution, the mass percent of the thalline is 15%-25%, the quality hundred of the gas generating compounds
Divide than being 0.3%-0.9%；
In the crosslinking agent, the mass percent of boric acid is 3%-5%, and the mass percent of calcium chloride is 2%-6%.
3. the preparation method of embedded immobilization microbial carrier as described in claim 1, which is characterized in that heating makes polyethylene
Alcohol is with the method that sodium alginate fully dissolves：Water added with polyvinyl alcohol and sodium alginate is heated to 100 DEG C -130 DEG C,
It is kept for 10 minutes to 50 minutes；
It is uniformly mixed the bacterium solution, the gas generating compounds solution, first gel solution by the way of stirring；
Second gel solution is added dropwise to from the ullage of the crosslinking agent using peristaltic pump of the end with outlet tube
In the crosslinking agent；
After second gel solution is instilled in the crosslinking agent, stand 15 hours or more.
4. the preparation method of embedded immobilization microbial carrier as described in claim 1, which is characterized in that the aerogenesis chemical combination
Object includes one or more in sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus, carbonic acid ammonia, ammonium hydrogencarbonate.
5. the preparation method of embedded immobilization microbial carrier as claimed in claim 4, which is characterized in that the aerogenesis chemical combination
Object is sodium bicarbonate.
6. the preparation method of embedded immobilization microbial carrier as described in claim 1, which is characterized in that further include：It provides
The embedded immobilization microbial carrier is placed in the buffer solution after impregnating, with water to the embedded immobilization by buffer solution
Microbe carrier is cleaned.
7. the preparation method of embedded immobilization microbial carrier as claimed in claim 6, which is characterized in that the embedding is solid
Surely change microbe carrier, which is placed in the buffer solution, impregnates 30 minutes to 2 hours；
The buffer solution is potassium dihydrogen phosphate, a concentration of 0.03mol/L-0.07mol/L of the potassium dihydrogen phosphate.
8. a kind of embedded immobilization microbial carrier, which is characterized in that using the embedding as described in any one of claim 1-7
The preparation method of fixed microorganism carrier is prepared.
9. a kind of sewage water treatment method, which is characterized in that including：Sewage containing nitrogenous compound and such as claim 8 are provided
The embedded immobilization microbial carrier, fixed microorganism includes the micro- life of denitrogenation in the embedded immobilization microbial carrier
Object adds the embedded immobilization microbial carrier in the sewage, using the embedded immobilization microbial carrier to institute
The nitrogenous compound stated in sewage is degraded.
10. sewage water treatment method as claimed in claim 9, which is characterized in that the temperature of the sewage is 20-40 DEG C；It is described
The pH value of sewage is 7-9；The volume ratio of the embedded immobilization microbial carrier and the sewage is 10%-30%；The dirt
Carbon-nitrogen ratio in water is 1-3.
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