The material and its methods for making and using same of ammonia nitrogen in a kind of deep removal water
One, technical field
The present invention relates to sanitary sewage secondary effluent, the advanced nitrogens of sludge with high silver, micro- pollution Landscape Water body.
Two, background technology
With the aggravation of water pollution, eutrophication generally occurs for China's surface water body.It is tighter this requires being carried out to sewage
The denitrogenation dephosphorizing of lattice is handled.Nitrogen in sanitary sewage secondary effluent, ground landscape water body mainly with ammonia, nitrate, nitrite,
The form of organic nitrogen exists, and phosphorus therein mainly exists in the form of orthophosphates and organophosphor.
Ammonia nitrogen is mineralized nitrogen mainly by microorganism nitrification in biological aerated filter in advanced water treatment at present
NO3-N and NO2-N nitrogen.There are several defects for the advanced treating of water for biological aerated filter technology:(1) in sanitary sewage
Organic nitrogen, ammonia nitrogen are largely converted into nitrate nitrogen in aerobic biochemical water process, and a part is in systems since denitrification is made
With nitrogen is converted into, the high nitrate nitrogen of valence is still remained in water, although the removal rate of ammonia nitrogen can reach 90% or more, total nitrogen
Removal rate is not high, generally in 20-40%, is also lacked at present for sanitary sewage Cheap highly effective denitrification denitrogenation technology and material;
(2) it needs to be aerated, since there are hydrostatic pressures, the wind pressure of Aeration fan is more demanding, and oxygenation utilization ratio is low, and energy consumption is higher;
(3) it also needs to be backwashed, to eliminate filtering material particle surface aging biological membranous layer, to eliminate gap and block.Moving-bed active sand skill
Art can not achieve the oxidation of ammonia nitrogen by denitrification denitrogenation, need to add carbon source to realize denitrification.
Patent CN201110397171.9 discloses a kind of processing method of domestic sewage advanced dephosphorization denitrogenation, is to boil
Mountain flour material is major ingredient, mix and be granulated by cementing material of cement after bio-filter stuffing is prepared, pass through intermittent biology
Filter tank reactor handles sanitary sewage.Since the patent system is not added with foaming agent, disadvantage in the process for granular filler
That to prepare material porosity not high, especially macropore gap is insufficient inside particle, cause microorganism particle internal load amount not
Foot further affects microorganism nitrification, the efficiency of denitrification denitrogenation effect.
Patent CN201110106007.8 discloses a kind of low-density zeolite biological aerated filter filling and preparation method thereof,
Its filler is the low-density zeolite biological aerated filter formed using expanded plastic particles as kernel, by shell of natural zeolite particle
Filler.The shortcomings that filler is:Expanded plastic particles are that the intensity of kernel is low, by pressure and particle from gravity be easy to cause with
The outer shell of natural zeolite composition is broken;Expanded plastic particles lack open gap, and microorganism can not enter foamed plastic
Apposition growth in intragranular core;Also lack macropore gap as outer shell using natural zeolite particle.This results in microorganism in filtrate
Intragranular section load amount is insufficient, affects microorganism nitrification, the efficiency of denitrification denitrogenation effect.
Three, invention content
The present invention is to provide ammonia nitrogen in a kind of deep removal water to avoid above-mentioned existing deficiencies in the technology
Material and its methods for making and using same.
The present invention solves technical problem, adopts the following technical scheme that:
The present invention discloses a kind of material of ammonia nitrogen in deep removal water first, and feature is:The deep removal water
The material of middle ammonia nitrogen is using natural zeolite powder as raw material, is foaming with aluminium powder, lime and surfactant using cement as binder
Agent, the zeolite air entrained concrete granular materials being prepared through dispensing, mixing, molding, cutting, steam press maintenance;Wherein:Natural boiling
Mountain flour, cement, foaming agent mass ratio be 100:15~20:5~10.
The zeolite air entrained concrete granular materials can selective ion exchange absorption water in ammonia nitrogen and nitre
Change microorganism.The grain size of the zeolite air entrained concrete granular materials is less than 1, open porosity in 10~30mm, apparent density
More than 40%.
The mass ratio for constituting the aluminium powder of the foaming agent, lime and surfactant is 1:20~100:10~30.
The present invention further discloses the preparation method of the material of ammonia nitrogen in above-mentioned deep removal water, feature be include
Following steps:
Natural zeolite is crushed, crosses 0.1mm sieves, obtains natural zeolite powder;According to the ratio by aluminium powder, lime and surfactant
Mixing obtains foaming agent;According to the ratio by natural zeolite powder, foaming agent and cement mixing, mixture is obtained;
It by mixture moulding by casting, cutting, is then placed in steam press maintenance kettle and conserves 10~20h, that is, obtain zeolite aerating
Concrete particle material.The temperature of steam press maintenance is 150~180 DEG C, and pressure is 10~12Mpa.
The invention also discloses the application process of the material of ammonia nitrogen in above-mentioned deep removal water, feature is:By zeolite
Air entrained concrete granular materials is loaded into denitrogenation processing pond as filler, and carries out microorganism colonization;After biofilm success, according to
Absorption phase, the emptied of water stage, air blast oxygenation the stage, water wash stage four-stage sequencing batch operation, to treatment sewage into
Row processing, makes water outlet ammonia nitrogen concentration of emission≤1.5mg/L;
The mode of the microorganism colonization is:Sewage treatment plants activated sludge suspension 20L, quiet heavy 10min is taken to abandon
Bottom sediment is removed, ammonium salt, which is added, makes ammonia nitrogen concentration reach 50mg/L, is oxygenated enrichment culture aerobic nitrification bacterium, obtains enrichment culture
Aerobic nitrification bacterium solution;It is full of accessing pending water in the container for accounting for denitrogenation processing pond body product 1/10th, is added into accessing pending water
Ammonia salt to ammonia nitrogen concentration is 50mg/L, the aerobic nitrification bacterium solution of the enrichment culture is then inoculated with into accessing pending water, oxygenation is simultaneously
So that ammonia nitrogen concentration in water is maintained 10~50mg/L by adding ammonia nitrogen, cultivates 3~4 days nitrification bacterium solutions to be spread cultivation;Institute
It states on the nitrification bacterium solution circulated sprinkling to the filler in denitrogenation processing pond to spread cultivation, so that ammonia nitrogen concentration in water is maintained by adding ammonia nitrogen
10~50mg/L, 3~4 angel's filler surfaces of cycle form stable nitrification biomembrane, you can according to absorption phase, emptied of water rank
Section, air blast oxygenation stage, water wash stage four-stage sequencing batch operation;
The step of absorption phase is:Filler is after microorganism colonization success in denitrogenation processing pond, by pending dirt
Water is continuously injected into denitrogenation processing pond, is controlled 0.5~3h of hydraulic detention time, is completed the processing for the treatment of sewage, make water outlet ammonia
Nitrogen discharged concentration≤1.5mg/L;
The step of emptied of water stage is:When denitrogenation processing pond be discharged ammonia nitrogen concentration of emission > 1.5mg/L when, stop into
Water empties the water in denitrogenation processing pond;
The air blast is the step of the oxygenation stage:After water in denitrogenation processing pond to be evacuated, by air blower from denitrogenation
1~2d of bottom blast of processing pond, realizes the regeneration of filler;
The step of water wash stage is:After air blast, the water wash denitrogenation processing pond of 1~2 times of volume is used
Interior filler, leacheate individually carry out denitrification denitrogenation processing after collecting;
After the water wash stage, function is restored in denitrogenation processing pond, carries out next periodic duty.
To leacheate carry out denitrification denitrogenation processing method be:Leacheate is stored in leacheate reservoir, to elution
Carbon source and denitrifying bacterium denitrogenation are added in liquid reservoir, is stood after stirring evenly, and complete denitrification denitrogenation processing, treated, and water is arranged
It puts;If pending water is sanitary sewage secondary treatment yielding water, also can denitrification denitrogenation be carried out to leacheate as follows
Processing:Leacheate is returned in sanitary sewage regulating reservoir, using the organic carbon in sanitary sewage as electron acceptor, in regulating reservoir
Complete denitrification denitrogenation processing.
The protrusion effect of the present invention is embodied in the following aspects:
1, using natural zeolite powder as primary raw material, addition binder, foaming agent through dispensing, mixing, are molded, cut the present invention
It cuts, zeolite air entrained concrete granular materials prepared by steam press maintenance, there is very high ammonium ion exchange selectivity and capacity, have
Lower apparent density and very high open porosity, extra-granular and inside all load nitrifying microorganisms, have and load micro- life
Effect that object amount is big, aerobic ammonia oxidation is efficient;And since granular materials grain size is larger, ischaemia is easily formed inside particle
And anaerobic zone, short distance nitration and Anammox denitrification can be played.
2, the operation in batch-type denitrogenation processing of the present invention pond is divided into absorption phase, emptied of water stage, air blast oxygenation stage, water
The elution stage;Batch-type denitrogenation processing pond Zhong Shui is emptying when air blast, and compared to for biological aerated filter, air blast oxygenation is not required to
Overcome the static pressure of water, system operation only to need the microkinetic of low-lift pump and low wind pressure air blast, runs low energy consumption.
3, present invention ammonia nitrogen in absorption phase is by filtering Adsorption water, while zeolite air entrained concrete granular materials
It is microorganism carrier again, and since particle diameter is larger, particle inside and outer surface attached biological film, due to microorganism generation
Thank to consumption dissolved oxygen, zeolite air entrained concrete granular materials has dissolving gradient from edge to center, detests at external aerobic, center
Based on aerobic bacteria, internal attached microbial is including good based on amphimicrobe, anaerobic bacteria for oxygen, surface and external attached microbial
Oxygen organic degradation bacteria, nitrifier, heterotrophic denitrifying Bacteria, anaerobic ammonia oxidizing bacteria etc..In absorption phase, aerobic nitrification bacterium utilizes water
Middle dissolved oxygen transform portion ammonia nitrogen is nitrate, and nitrate and ammonia nitrogen are converted by the anaerobic ammonia oxidizing bacteria of electron acceptor of nitrate
For nitrogen, it is nitrogen that the synergistic effect of these microorganisms, which has converted the ammonia nitrogen of part,.Unconverted complete ammonia nitrogen is with ion exchange
Form is fixed in zeolite air entrained concrete granular materials.In above-mentioned zeolite air entrained concrete granular materials the nitrification of microorganism and
Denitrification denitrogenation extends granular materials ion exchange ammonia nitrogen time of break-through.
4, it exchanges and inhales in the oxidation by nitrobacteria zeolite intermediate ion of air blast oxygenation regeneration stage above-mentioned material surfaces externally and internally load
Attached ammonia nitrogen is nitrate, restores ion exchanging function of the zeolite air entrained concrete granular materials to ammonia nitrogen in water later, realizes
The regeneration of zeolite air entrained concrete granular materials.Its air blast oxygenation is that the water in emptying denitrogenation processing pond is run,
Compared with traditional biological aerated filter, its advantage is that the intergranular pore of zeolite air entrained concrete granular materials is big, no hydrostatic pressing
Power, required air blower wind pressure is small, low energy consumption, efficiency of oxygen supply is high.
5, the NO3-N and NO2-N that the removal blasting regeneration stage in water wash stage generates is collected leacheate and is individually located
Reason, solves the problems, such as that traditional aeration biofilter only completes nitrification and is not carried out denitrogenation.
Four, specific implementation mode
Embodiment 1
This implementation prepares zeolite air entrained concrete granular materials as follows first:
Natural clinoptilolite ore is selected, 0.1mm sieves was crushed, and obtained natural zeolite powder;
Mass ratio according to aluminium powder, pulverized limestone and surfactant is 1:50:10 ratio weighs raw material, after mixing
As foaming agent;
Weigh 100 parts of natural zeolite powders, 15 parts of cement are added in agitator, add water stirring as underflow shape and maintaining to starch
Liquid temperature 45 C adds 5 parts of foaming agents and stirs evenly before pouring;
Just foster room carries out the pre-hardening 1.5h that gets angry to cast rear mold feeding, just supports rear green body steel wire cutting machine from longitudinal and transverse, water
The block that three directions are cut into 10~30mm is put down, is then put into steam press maintenance kettle under 12Mpa pressure, at a temperature of 180 DEG C
Steam curing 12h obtains zeolite air entrained concrete granular materials;
Zeolite air entrained concrete granular materials prepared by the present embodiment is characterized in, can selective ion exchange absorption
Ammonia nitrogen in water, but high-efficient carrier nitrification, denitrifying microorganism, apparent density are less than 1, open porosity and are more than 40%.
Using the water outlet of sanitary sewage two stage treatment as the object of advanced nitrogen, the zeolite air entrained concrete of the present embodiment is utilized
The method that granular materials carries out denitrogenation of waste water is as follows:
Zeolite air entrained concrete granular materials is loaded into denitrogenation processing pond, the water outlet with sanitary sewage two stage treatment is
The object of advanced nitrogen, structure batch-type denitrogenation processing pond, then carries out microorganism colonization culture;
The step of microorganism colonization is:Sewage treatment plants activated sludge suspension 20L, quiet heavy 10min is taken to discard bottom
Portion's sediment, ammonium salt, which is added, makes ammonia nitrogen concentration reach 50mg/L, is oxygenated enrichment culture aerobic nitrification bacterium, obtains the aerobic of enrichment culture
Nitrify bacterium solution;It is full of accessing pending water in the container for accounting for denitrogenation processing pond body product 1/10th, ammonia salt is added into accessing pending water
It is 50mg/L to ammonia nitrogen concentration, the aerobic nitrification bacterium solution of enrichment culture is then inoculated with into accessing pending water, is oxygenated and by adding
Ammonia nitrogen makes ammonia nitrogen concentration in water maintain 10-50mg/L, cultivates the 3-4 days nitrification bacterium solutions to be spread cultivation;The nitre to spread cultivation
Change on bacterium solution circulated sprinkling to the filler in denitrogenation processing pond, so that ammonia nitrogen concentration in water is maintained 10-50mg/L by adding ammonia nitrogen,
3~4 angel's filler surfaces of cycle form stable nitrification biomembrane.
Denitrogenation processing pond after microorganism colonization maturation is drenched according to absorption phase, emptied of water stage, air blast oxygenation stage, water
Stage four-stage sequencing batch operation is washed, it is specific as follows:
Absorption phase:Treatment sewage is continuously injected into de- by filler after microorganism colonization success in denitrogenation processing pond
In nitrogen processing pond, hydraulic detention time 1h is controlled, the processing for the treatment of sewage is completed, makes water outlet ammonia nitrogen concentration of emission≤1.5mg/
L;
The emptied of water stage:When denitrogenation processing pond is discharged ammonia nitrogen concentration of emission > 1.5mg/L, stop water inlet, empties denitrogenation
Water in processing pond;
Air blast is oxygenated the stage:After water in denitrogenation processing pond to be evacuated, by air blower from the bottom in denitrogenation processing pond
Air blast 1d, aerobic ammonia oxidation microorganism make zeolite absorption mineralized nitrogen be that NO3-N and NO2-N realizes regeneration;
The water wash stage:After air blast, the filler in water wash denitrogenation processing pond accumulated using 1 times of pond body, removal
The NO3-N and NO2-N of generation.Leacheate returns in sanitary sewage regulating reservoir after leacheate is collected, in sanitary sewage
Organic carbon be electron acceptor, in regulating reservoir complete denitrification denitrogenation processing.
After the water wash stage, the function of ion exchange ammonia nitrogen is restored in denitrogenation processing pond, restarts water pump and carries out next period
Operation.
Embodiment 2
This implementation prepares zeolite air entrained concrete granular materials as follows first:
Natural clinoptilolite ore is selected, 0.1mm sieves was crushed, and obtained natural zeolite powder;
Mass ratio according to aluminium powder, pulverized limestone and surfactant is 1:80:20 ratio weighs raw material, after mixing
As foaming agent;
Weigh 100 parts of natural zeolite powders, 15 parts of cement are added in agitator, add water stirring as underflow shape and maintaining to starch
Liquid temperature 45 C adds 10 parts of foaming agents and stirs evenly before pouring;
Cast rear mold is sent into just foster room and carries out the pre-hardening 2h that gets angry, and green body steel wire cutting machine is from longitudinal and transverse, horizontal after just supporting
Three directions are cut into the block of 10~30mm, are then put into steam press maintenance kettle under 12Mpa pressure, 180 DEG C of steam curings
10h obtains zeolite air entrained concrete granular materials.
Zeolite air entrained concrete granular materials prepared by the present embodiment is characterized in, can selective ion exchange absorption
Ammonia nitrogen in water, but high-efficient carrier nitrification, denitrifying microorganism, apparent density are less than 1, open porosity and are more than 40%.
Using the landscape water of eutrophication as the object of advanced nitrogen, the zeolite air entrained concrete granular material of the present embodiment is utilized
The method that material carries out denitrogenation of waste water is as follows:
Zeolite air entrained concrete granular materials is loaded into advanced nitrogen water treating pond, is with the landscape water of eutrophication
The object of advanced nitrogen, structure batch-type denitrogenation processing pond, then carries out microorganism colonization culture;
The step of microorganism colonization is:Sewage treatment plants activated sludge suspension 20L, quiet heavy 10min is taken to discard bottom
Portion's sediment, ammonium salt, which is added, makes ammonia nitrogen concentration reach 50mg/L, is oxygenated enrichment culture aerobic nitrification bacterium, obtains the aerobic of enrichment culture
Nitrify bacterium solution;It is full of accessing pending water in the container for accounting for denitrogenation processing pond body product 1/10th, ammonia salt is added into accessing pending water
It is 50mg/L to ammonia nitrogen concentration, the aerobic nitrification bacterium solution of enrichment culture is then inoculated with into accessing pending water, is oxygenated and by adding
Ammonia nitrogen makes ammonia nitrogen concentration in water maintain 10-50mg/L, cultivates the 3-4 days nitrification bacterium solutions to be spread cultivation;The nitre to spread cultivation
Change on bacterium solution circulated sprinkling to the filler in denitrogenation processing pond, so that ammonia nitrogen concentration in water is maintained 10-50mg/L by adding ammonia nitrogen,
3~4 angel's filler surfaces of cycle form stable nitrification biomembrane.
Denitrogenation processing pond after microorganism colonization maturation is drenched according to absorption phase, emptied of water stage, air blast oxygenation stage, water
Stage four-stage sequencing batch operation is washed, it is specific as follows:
Absorption phase:Treatment sewage is continuously injected into de- by filler after microorganism colonization success in denitrogenation processing pond
In nitrogen processing pond, hydraulic detention time 1h is controlled, the processing for the treatment of sewage is completed, makes water outlet ammonia nitrogen concentration of emission≤1.5mg/
L;
The emptied of water stage:When denitrogenation processing pond is discharged ammonia nitrogen concentration of emission > 1.5mg/L, stop water inlet, empties denitrogenation
Water in processing pond;
Air blast is oxygenated the stage:After water in denitrogenation processing pond to be evacuated, by air blower from the bottom in denitrogenation processing pond
Air blast 1d, aerobic ammonia oxidation microorganism make zeolite absorption mineralized nitrogen be that NO3-N and NO2-N realizes regeneration;
The water wash stage:After air blast, the filler in water wash denitrogenation processing pond accumulated using 1 times of pond body, removal
The NO3-N and NO2-N of generation.Leacheate is collected and is stored in leacheate reservoir, and grape is added into leacheate reservoir
Sugar and denitrifying bacterium denitrogenation make carbon-nitrogen ratio in water close to 3:1,1 week is stood after stirring evenly, completes denitrification denitrogenation processing,
Supernatant discharges after processing.
After the water wash stage, the function of ion exchange ammonia nitrogen is restored in denitrogenation processing pond, restarts water pump and carries out next period
Operation.