CN105060542B - Method for recovering nitrogen and phosphorus in anaerobic digestion solution of municipal sludge and special device for method - Google Patents
Method for recovering nitrogen and phosphorus in anaerobic digestion solution of municipal sludge and special device for method Download PDFInfo
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Abstract
The invention discloses a method for recovering nitrogen and phosphorus in an anaerobic digestion solution of municipal sludge and a special device for the method. The method comprises steps as follows: the anaerobic digestion solution of the municipal sludge is pre-treated; MAP (MgNH4PO4.6H2O) is subjected to pyrolysis in a pyrolysis adsorption column; ammonia nitrogen in the anaerobic digestion solution is adsorbed in the pyrolysis adsorption column; phosphorus in an effluent after adsorption is recovered; recovered precipitates are transferred to the pyrolysis adsorption column for pyrolysis and regeneration after being dried, and ammonia nitrogen is recovered; nitrogen and phosphorus in the anaerobic digestion solution is recovered circularly. A dry type pyrolysis method is adopted under the low-temperature condition, ammonia nitrogen in the anaerobic digestion solution are separated and concentrated, and energy consumption of a reaction is reduced; an integrated pyrolysis and adsorption device is adopted, adjustment and control are convenient, and operation and maintenance are facilitated; the recovery efficiency of nitrogen and phosphorus is high in the recovery process; a phosphorus source is not required to be supplemented in the recovery process, and the cost of reagents for recovery of nutrient elements is greatly reduced; the content of organic matters and heavy metal in nutrient element recovery products is extremely low, and the method and the special device have higher economic value.
Description
Technical field
The invention belongs to city sewage sludge reclamation technical field, it is related to the process of urban mud anaerobic digestion solution and resource is returned
Receiving method is and in particular to the method for nitrogen phosphorus and its special purpose device in a kind of recovery urban mud anaerobic digestion solution.
Background technology
During " 12 ", China will implement overall control to the ammonia nitrogen discharge in key industry and key area, and first
Secondary by ammonia nitrogen include the binding indicator system strengthen supervision, be distinctly claimed reduction of discharging 10%.According to 2013, " Chinese environmental situation was public
Report " count, inorganic nitrogen and reactive phosphate are classified as main contamination index by national four big sea area immediate offshore areas；National 423 day
Water amount of blowdown is more than ammonia nitrogen total emission volumn in 100 cubic metres of in line sea industrial pollution source, domestic pollution source and comprehensive sewage draining exit
For 1.69 ten thousand tons, total phosphorus total emission volumn is 2841 tons.Substantial amounts of nitrogen phosphorus enters in water body, not only pollutes environment, simultaneously also unrestrained
Substantial amounts of precious resources are taken.
The meaning reclaiming nitrogen phosphorus from sewage is: (1) reduces nitrogen phosphorus to discharge into water, prevents body eutrophication；(2)
In sewage, recovery of nitrogen and phosphorus can efficiently reduce the load that sewage treatment plant processes nitrogen phosphorus, reduces the processing cost of sewage, at raising
Reason effect；(3) recovery product can provide new nitrogen phosphorus raw material for commercial production, has saved nitrogen phosphor resource, meeting nitrogen phosphor resource can
The requirement of sustainable utilization；(4) some recovery of nitrogen and phosphorus products have certain market potential value, can be directly used for slow-release fertilizer etc..
The process research reclaiming nitrogen phosphorus at present from sewage is more, including the sedimentation method, crystallization process, absorption method, ion
Exchange process etc..These methods or because the response rate is not high, or recovery product quality is low, or recovery process is complicated and cost recovery is higher
And fail to be widely used.
Liu Dapeng etc. adds na using map method2hpo4·12h2O and mgcl2·6h2O removes the high concentration in coking chemical waste water
Ammonia nitrogen, works as n(mg2+): n(nh4 +): n(po4 3-) it is 1.3: 1: 0.9, under conditions of optimal ph value 8.5 ~ 10.0, nh4 +- n removes
Rate is more than 96%, and remaining phosphorus mass concentration is less than 20mg/l；Zhang Yanyan etc. utilizes map method to process simulation pig farm biogas slurry, ammonia nitrogen
Mass concentration is 350～750mg/l, and the mass concentration of soluble phosphate is 55mg/l, according to n(mg): n(p)=1.5 add
mgcl2, when reacting ph=10, tp removal rate is up to 97%, ammonia nitrogen removal frank only 20%；Li Shisong etc. is based on map method seawater coagulation
Process Nitrogen-and Phosphorus-containing waste water, to nh4 +- n initial concentration is respectively 115.69mg/l, 274.41 mg/l, the nitrogen phosphorus of 505.69 mg/l
Waste water is processed, by adding nah2po4Control n: p mol ratio to be 1: 1, adjust solution with sodium hydroxide solution and hcl
Ph value, to 9.5, works as nh4 +During the purity highest of-n clearance and map, nh4 +- n clearance is 68.32 ~ 73.35%；Xiang Xuemin etc.
Adopt hot acid combined method to process mud to discharge phosphorus, and ammonium chloride is added as magnesium source using sea water simultaneously and returned with ammoniomagnesium phosphate form
Receive the phosphorus in rich phosphorus supernatant, positive phosphorous recovery is up to 94.89%；The research such as battistoni is reclaimed dirty using sea water as magnesium source
, it is not necessary to add chemical agent, about 70% soluble phosphate can precipitate recovery for phosphorus in mud supernatant liquid from sludge dehydration and nitrogen；
Korchef etc. have studied mg2+、po4 3-、nh4 +Effect during ammoniomagnesium phosphate reclaims phosphorus, finds nh4 +Concentration by
When 18.92mg/l increases to 227.27mg/l, phosphorous recovery increases to 75% by 21%；Jaffer etc. is to phosphorus concentration 167mg/l's
When finding ph9.0, mg/p mol ratio for 1.05 in the pilot plant test of waste water reclamation phosphorus, phosphorous recovery can reach 97%.
In sum, the above method processing and reclaiming nitrogen phosphorus based on map method is primarily present some problem following: (1) no
During using sea water as magnesium source, magnesium salt dosage is big, and reagent cost is high；(2), when using sea water as magnesium source, generally require to supplement phosphorus
Source, simultaneously as k+、ca2+And mg2+Introducing, the purity of recovery product can accordingly decline；(3) when the same period reclaiming nitrogen phosphorus, past
Toward can not obtain higher recovery of nitrogen and phosphorus rate simultaneously；(4) phosphor resource reclaiming fails recycling in follow-up recovery of nitrogen and phosphorus.
Therefore, how reduce medicament expense with while, improve recovery of nitrogen and phosphorus rate and recycle recovery phosphor resource the problems such as
Become the study hotspot of recovery of nitrogen and phosphorus.
Content of the invention
Goal of the invention: for the deficiencies in the prior art, it is an object of the invention to provide a kind of reclaim municipal sludge
The method of nitrogen phosphorus in anaerobic digestion solution, the characteristic using map and its thermal decomposition product reclaims nitrogen from urban mud anaerobic digestion solution
Phosphor resource simultaneously recycles.It is a further object of the present invention to provide nitrogen phosphorus in a kind of above-mentioned recovery urban mud anaerobic digestion solution
The special purpose device of method.
Technical scheme: in order to realize foregoing invention purpose, the technical solution used in the present invention is:
A kind of method of nitrogen phosphorus in recovery urban mud anaerobic digestion solution: in pyrolysis adsorption column, first to map
(mgnh4po4·6h2O) carry out pyrolysis and obtain absorption material, reclaim the ammonia that pyrolysis is discharged；Then pass to upper prop anaerobic digestion
Liquid carries out adsorption treatment, obtains effluent；Ammonia nitrogen concentration in detection effluent, when ammonia nitrogen concentration is more than 0, stops absorption,
First supplement fresh feed, then be pyrolyzed, reclaim the ammonia that pyrolysis is discharged, then proceed to absorption, detection is circulated operation；Its
In, fresh feed is to add mgcl in the mixed liquor with pretreated anaerobic digestion solution for the effluent2It is heavy that solution is obtained
Starch raw material after drying；In the ammonia reclaiming and final pyrolysis adsorption column, material is recovery of nitrogen and phosphorus product.
The described method reclaiming nitrogen phosphorus in urban mud anaerobic digestion solution, comprises the following steps:
(1) urban mud anaerobic digestion solution is filtered, obtain anaerobic digestion solution after filter, then detested with after hydrochloric acid regulation filter
Oxygen Digestive system ph to 3.5 ~ 4.0, obtains pretreated anaerobic digestion solution；Adjust pretreated anaerobism with sodium hydroxide solution
The ph of Digestive system is 8.0 ~ 10.0, obtains upper prop anaerobic digestion solution；
(2) pyrolysis temperature is controlled to be 80 ~ 100 DEG C, pyrolysis time 1 ~ 3h, ventilation/quality is 1.2 ~ 9.6m3·h-1·
kg-1, quality/contact area be 0.78 ~ 2.17kg m-2, pyrolysis adsorption column in map is pyrolyzed, the ammonia steaming by
Absorption bottle equipped with dilute sulfuric acid absorbs；
(3) upper prop anaerobic digestion solution is passed through pyrolysis adsorption column, carries out dropping streaming operation, fortune with the flow velocity of 1 ~ 5bv/h
Controlling adsorption reaction ph with sodium hydroxide solution between the departure date is 8.0 ~ 10.0, obtains product collect effluent after ammonia nitrogen absorption；
(4) press reaction phosphorus nitrogen mol ratio and add effluent in step (3) the pre- place in step (1) for 0.8 ~ 1.2: 1
In anaerobic digestion solution after reason, obtain mixed liquor；Add mgcl by reaction magnesium nitrogen mol ratio for 1.5 ~ 2.0: 12Solution is to mixing
In liquid；With sodium hydroxide solution control reaction ph be 7.0 ~ 10.0, under 200rpm rotating speed react 30min, obtain precipitate and
Supernatant；
(5) press the continuous absorption of step (3), the ammonia nitrogen concentration in detection effluent, when ammonia nitrogen concentration is more than 0, stop inhaling
Attached；
(6) dry precipitate, obtain fresh feed；First transfer fresh raw material to pyrolysis adsorption column in, then by step (2) ~
(5) it is circulated operation；In the ammonia reclaiming and final pyrolysis adsorption column, material is recovery of nitrogen and phosphorus product.
In step (1), the composite fibre membrane filtration being 0.45 μm using aperture removes in urban mud anaerobic digestion solution
Float and partly organic matter.
In step (1), adjusting anaerobic digestion solution ph after filter using the hydrochloric acid for 2.0mol/l for the concentration is 4.0；Using concentration
The ph that sodium hydroxide solution for 0.2mol/l adjusts pretreated anaerobic digestion solution is 10.0.
In step (3), controlling adsorption reaction ph using the sodium hydroxide solution for 0.2mol/l for the concentration is 10.0；Ammonia nitrogen is inhaled
Attached product Nitrogen content is with nh4 +- n is calculated as 4 ~ 10%, and phosphorous rate is with p2o5It is calculated as 24 ~ 41%, rate containing magnesium is calculated as 15 ~ 36% with mgo.
In step (4), controlling reaction ph using the sodium hydroxide solution for 4.0mol/l for the concentration is 9.0.
In step (4), reaction phosphorus nitrogen mol ratio is 1.0 ~ 1.1: 1, and reaction magnesium nitrogen mol ratio is 1.8 ~ 2.0: 1, reacts ph
For 9.0.
In step (4), in mixed liquor, the response rate of nitrogen and phosphorus respectively reaches 91% and more than 92%；Fresh feed Nitrogen content
With nh4 +- n is calculated as 4 ~ 9%, and phosphorous rate is with p2o5It is calculated as 20 ~ 38%, rate containing magnesium is calculated as 17 ~ 44% with mgo.
In step (6), dry sedimentary temperature and be 40 ~ 45 DEG C.
The described special purpose device reclaiming the method for nitrogen phosphorus in urban mud anaerobic digestion solution, including thermostatic water-circulator bath pot
(1), thermal plume of air (2), pyrolysis adsorption column (3), air pump (4), desiccant (6), absorption bottle (7), upper prop anaerobic digestion solution store up
Tank (8), pretreated anaerobic digestion liquid storage tank (18), diluted alkaline flow container (11), mgcl2Solution reservoir (21), concentrated base flow container
(24), nutrient reclaims retort (15), the electrode probe (17) of ph meter (16), ph meter, feed box (30)；Described is super
Thermostat water bath (1) is connected with thermal plume of air (2), and described thermal plume of air (2) is connected with pyrolysis adsorption column (3), described gas
Pump (4), glass rotameter (5) are connected with thermal plume of air (2), set desiccant (6) in pyrolysis adsorption column (3), described
Absorption bottle (7) is connected with pyrolysis adsorption column (3), described upper prop anaerobic digestion liquid storage tank (8) and pyrolysis adsorption column (3) phase
Even, described pyrolysis adsorption column (3) effluent, concentrated base flow container (24), the electrode probe (17) of ph meter, pretreated anaerobism disappear
Change liquid storage tank (18) and mgcl2Solution reservoir (21) all reclaims retort (15) with nutrient and is connected.
Ammoniomagnesium phosphate, also known as map, is commonly called as guanite, and chemical formula is mgnh4po4·6h2O, is a kind of the slow of function admirable
Release fertilizer.
As time goes on ammoniomagnesium phosphate can lose water of crystallization, partially or completely after temperature rises to certain limit
nh4 +- n, is decomposed into mghpo4, mg3(po4)2, mg2p2o7Mixture.And mghpo4With mg3(po4)2To nh4 +- n has suction
Attached function, wherein mghpo4To nh4 +The adsorption effect of-n is very notable.By being pyrolyzed map, obtain thermal decomposition product, can be for reclaiming
Nutrient in anaerobic digestion solution provides suitable raw material.
Municipal sludge, after Normal Temperature Anaerobic Digestion, takes anaerobic digestion solution to stand, the composite fibre being 0.45 μm using aperture
Anaerobic digestion solution after membrane filtration is transparent yellowish, containing abundant dissolubility orthophosphate, contains more highly concentrated simultaneously
The ammonia nitrogen of degree, and containing a small amount of calcium ion, magnesium ion, sodium ion and chloride ion etc..Anaerobic digestion solution cod concentration after filter
140.8 ~ 372.7mg/l, total organic carbon toc concentration be 16.4 ~ 37.7mg/l, dissolubility orthophosphate concentration be 38.4 ~
132.1mg/l, ammonia nitrogen concentration is 117.0 ~ 465.3mg/l, ca2+Concentration is 20.3 ~ 65.3mg/l, k+Concentration be 34.2 ~
79.8mg/l, mg2+Concentration is 57.8 ~ 65.8mg/l.
Anaerobic digestion solution after acidizing pretreatment is flowed through map thermal decomposition product, using the hydroxide for 0.2mol/l for the concentration
It is 8.0 ~ 10.0 that sodium solution controls adsorption reaction ph, obtains product collect effluent after ammonia nitrogen absorption.Under dominant response can use
Formula represents:
mg2++hpo4 2-+nh4 ++6h2o⇋mgnh4po4·6h2o↓+h+
Along with the carrying out of map reaction of formation, constantly there is h+Release, leads to solution ph to decline, the carrying out of suppression reaction.
Additionally, the mg of excess2+It is also possible to and oh-Complexation, generation complex [mg(oh)]+, equally also can release h+, make ph further
Reduce.Therefore, it is necessary to the h adding in alkali and producing+, reaction just can be made to carry out to the direction being conducive to generating map.Keep absorption anti-
Answer ph can form more magnesium ammonium phosphate sediments, keep adsorption reaction ph can improve the ammonia nitrogen response rate of anaerobic digestion solution.
The dissolubility orthophosphate in effluent after ammonia nitrogen recovery and mg2+Concentration be respectively 110.5 ~ 226.9mg/l and
85.5~170.3mg/l.Add the effluent after ammonia nitrogen reclaims according to reaction phosphorus nitrogen mol ratio 0.8 ~ 1.2: 1 to pretreated
In anaerobic digestion solution, form mixed liquor, add part mgcl according to reaction magnesium nitrogen mol ratio 1.5 ~ 2.0: 1 simultaneously2Solution, adopts
Concentration is that the sodium hydroxide solution of 4.0mol/l controls reaction ph 7.0 ~ 10.0, obtains precipitate, dry precipitate obtain new
Fresh raw material；In mixed liquor, the response rate of nitrogen and phosphorus respectively reaches 91% and more than 92%.Obtain the dominant response of this fresh feed
Can be represented by the formula:
mg2++po4 3-+nh4 ++6h2o⇋mgnh4po4·6h2o↓
In nutrient removal process, reaction phosphorus nitrogen mol ratio, reaction magnesium nitrogen mol ratio and reaction ph have to recovery of nitrogen and phosphorus rate
Material impact.Nitrogen phosphorus magnesium ion initial concentration in mixed liquor before reaction phosphorus nitrogen mol ratio, reaction magnesium nitrogen mol ratio decision reaction；Instead
Ph is answered to determine the existence form of phosphate radical in mixed liquor.
Using fourier infrared (ftir), x-ray diffraction (xrd), inductively coupled plasma direct reading spectrometry (icp) and sweep
Retouch ultramicroscope (sem) fresh feed property to be analyzed characterize with analysis means such as power spectrums (eds).Fresh feed is almost
Without organic matter；In addition to containing ca, mg, also contain the metallic elements such as minimal amount of na, al, fe, content of beary metal is extremely low；Fresh former
Material, can carry out again being pyrolyzed, adsorb, recycle.
Beneficial effect: compared with the method for nutrient in existing recovery urban mud anaerobic digestion solution, the present invention has
Some outstanding advantages include: the method 1) adopting dry type pyrolysis under cryogenic, both achieved nitrogen in anaerobic digestion solution point
From concentration, decrease energy consumption of reaction again；2) using the device of integration pyrolysis and absorption when running, regulation and control are convenient, easily operated
Safeguard；3) efficiency that nitrogen phosphorus reclaims simultaneously is higher, respectively reaches 91% and more than 92%；4) removal process need not supplement phosphorus source,
After nutrient reclaims, product can reuse during recovery of nitrogen and phosphorus；5) in final pyrolysis adsorption column, material can be used as one
The rich rock phosphate in powder planting function admirable is discharged.
Brief description
Fig. 1 is the schematic diagram reclaiming the special purpose device of method of nitrogen phosphorus in urban mud anaerobic digestion solution.
Specific embodiment
The present invention is further illustrated with specific embodiment below in conjunction with the accompanying drawings.
As shown in figure 1, being the special purpose device reclaiming the method for nitrogen phosphorus in urban mud anaerobic digestion solution of the present invention, including
Thermostatic water-circulator bath pot 1, thermal plume of air 2, pyrolysis adsorption column 3, air pump 4, glass rotameter 5, desiccant 6, absorption bottle 7,
Upper prop anaerobic digestion liquid storage tank 8, upper prop anaerobic digestion fluid supply pump 9, upper prop anaerobic digestion hydraulic control valve 10, sig water
Tank 11, diluted alkaline fluid supply pump 12, diluted alkaline hydraulic control valve 13, magnetic stirring apparatuss 14, nutrient reclaim retort 15, ph meter 16,
The electrode probe 17 of ph meter, pretreated anaerobic digestion liquid storage tank 18, pretreated anaerobic digestion fluid supply pump 19, pre- place
Anaerobic digestion hydraulic control valve 20 after reason, mgcl2Solution reservoir 21, mgcl2Solution supply pump 22, mgcl2Solution control valve 23,
Concentrated base flow container 24, concentrated base fluid supply pump 25, concentrated base hydraulic control valve 26, pyrolysis absorption raw material 27, pyrolysis adsorption column filter sand core 28,
Thermal plume of air filters core 29, feed box 30.This device passes through the temperature that thermostatic water-circulator bath pot 1 controls heating, in recirculated water
Entrance connects thermal plume of air 2, connects the pyrolysis adsorption column 3 equipped with pyrolysis absorption raw material at circulating water outlet, air pump 4 supply
Air through glass rotameter 5 metering enter thermal plume of air 2 hot-air, via pyrolysis adsorption column 3 by map be pyrolyzed life
The nh becoming3Bring the absorption bottle 7 connecting equipped with dilute sulfuric acid into, desiccant 6 is used for avoiding the impact of pyrogenous origin water vapour.Pyrolysis
After the completion of close thermostatic water-circulator bath pot 1, after pyrolysis adsorption column 3 be cooled to room temperature after, upper prop anaerobic digestion solution is used by upper prop
Anaerobic digestion fluid supply pump 9 squeezes into pyrolysis adsorption column 3, and sodium hydroxide sig water is squeezed into by diluted alkaline fluid supply pump 12 simultaneously, obtains
Pyrolysis absorption raw material 27, effluent flows into nutrient and reclaims retort 15, and pretreated anaerobic digestion solution is by advance simultaneously
Anaerobic digestion fluid supply pump 19 after reason, mgcl2Solution is by mgcl2Solution supply pump 22, sodium hydroxide high alkali liquid are supplied by high alkali liquid
Squeeze into nutrient to pump 25 and reclaim retort 15, adjust the rotating speed of magnetic stirring apparatuss 14, reaction ph is controlled by ph meter 16, instead
Mixed system after the completion of answering pours feed box 30 into, and the precipitate after solid-liquid separation obtains fresh feed after drying sharp as repeating
Raw material is adsorbed in pyrolysis, transfers in pyrolysis adsorption column 3, is mixed with pyrolysis absorption raw material 27, carries out again being pyrolyzed, inhales
Attached, circulate operation.
Molybdenum-antimony anti-spectrophotometric method, Berthelot spectrophotometry, the chromatography of ions and potassium dichromate method is used to measure respectively
Dissolubility orthophosphate (sop, in terms of the p) concentration of effluent, ammonia nitrogen (nh in following embodiment4 +- n) concentration, magnesium ion be dense
Degree and cod concentration.
Phosphorous rate, Nitrogen content and the calculating process of rate containing magnesium that raw material is adsorbed in pyrolysis in following embodiment are described as follows:
Accurately weigh pyrolysis m gram of the raw material of absorption of 40 ~ 45 DEG C of drying, be dissolved completely in v milliliter dilute hydrochloric acid, use molybdenum respectively
The anti-spectrophotography of antimony, Berthelot spectrophotometry and this solution of ion-chromatographic determination dissolubility orthophosphate (sop,
Counted with p) concentration is as c1Mg/l, ammonia nitrogen concentration are c2Mg/l and magnesium ion concentration c3mg/l.Then, the phosphorous quality of m gram of product is (c1
× v ÷ 1000) milligram, nitrogenous quality is (c2× v ÷ 1000) milligram is (c containing magnesia amount3× v ÷ 1000) milligram.
The pyrolysis absorption phosphorous rate of raw material is with p2o5Meter=[(c1× v ÷ 1000) × (142 ÷ 62)] ÷ (m × 1000) ×
100%；
Pyrolysis absorption raw material Nitrogen content is with nh4 +- n meter=(c2× v ÷ 1000) ÷ (m × 1000) × 100%；
Pyrolysis absorption raw material rate containing magnesium in terms of mgo=[(c3× v ÷ 1000) × (40 ÷ 24)] ÷ (m × 1000) ×
100%.
Embodiment 1
Map is dried standby to constant weight sealing preserve at 40 ~ 45 DEG C.
Take map about 6.2g(1bv=10ml) it is placed in pyrolysis adsorption column, control 100 DEG C of pyrolysis temperature, pyrolysis time 2h, lead to
Tolerance/quality is 2.4 m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, the ammonia nitrogen amount of removing is 66.8mg.
, after Normal Temperature Anaerobic Digestion, the composite fibre membrane filtration being 0.45 μm using aperture, after obtaining filter for municipal sludge
Anaerobic digestion solution, adjusting anaerobic digestion solution ph after filter with the hydrochloric acid of 2.0mol/l is 3.5 ~ 4.0, obtains pretreated anaerobism and disappears
Change liquid, recording initial cod concentration is 194.1mg/l, initial nh4 +- n, sop and magnesium ion concentration respectively 173.7mg/l,
46.8mg/l and 32.5mg/l.
Adjusting pretreated anaerobic digestion solution ph with the sodium hydroxide solution of 4.0mol/l is 10.0, obtains upper prop with detesting
Oxygen Digestive system, is carried out dropping streaming and running adsorbing ammonia nitrogen in upper prop anaerobic digestion solution with the flow velocity of 2bv/h, is supplied by sig water
Pump is continuously replenished the sodium hydroxide solution of 0.2mol/l, and it is 10.0 that run duration controls adsorption reaction ph, collects effluent, absorption
After the completion of obtain ammonia nitrogen absorption after product.The cod mean concentration recording effluent is 172.1mg/l；nh4 +The mean concentration of-n is
1.1mg/l；The mean concentration of sop is 202.1mg/l；The mean concentration of magnesium ion is 239.9mg/l；Upper prop anaerobic digestion solution
Treating capacity reaches 28bv.
Dry product after ammonia nitrogen absorption at 40 ~ 45 DEG C, measure through analysis, after ammonia nitrogen absorption, the phosphorous rate of product is 31.9%,
Nitrogen content is 4.3%, and rate containing magnesium is 19.3%, and in product after ammonia nitrogen absorption, magnesium hydroxide and magnesium pyrophosphate composition are less, hardly
Containing organic and heavy metal.
By reaction phosphorus nitrogen mol ratio 1.0: 1, pretreated anaerobic digestion solution is added in obtained effluent, obtains
Mixed liquor；Add part mgcl by reaction magnesium nitrogen mol ratio 1.8: 12Solution is in mixed liquor；Molten with 4.0mol/l sodium hydroxide
Hydraulic control system reaction ph is 9.0, reacts 30min, obtain precipitate and supernatant under 200rpm rotating speed；The nh of supernatant4 +- n is dense
Spend for 12.8mg/l, the concentration of sop is 10.1mg/l.
Precipitate is dried at 40 ~ 45 DEG C, obtains fresh feed.Measure through analysis, the phosphorous rate of fresh feed is
26.4%, Nitrogen content is 4.6%, and rate containing magnesium is 18.2%, and fresh feed magnesium hydroxide seldom, is practically free of organic matter and heavy metal.
Fresh feed is transferred in pyrolysis adsorption column, for next pyrolysis.
Embodiment 2
Take appropriate map to be placed in pyrolysis adsorption column, control 80 DEG C of pyrolysis temperature, pyrolysis time 2h, ventilation/quality is
2.4 m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, obtain the ratio that the ammonia-nitrogen content steaming accounts for map nitrogen content
The thermal decomposition product for 17.7% for the example.
Embodiment 3
Take appropriate map to be placed in pyrolysis adsorption column, control 90 DEG C of pyrolysis temperature, pyrolysis time 2h, ventilation/quality is
4.8 m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, obtain the ratio that the ammonia-nitrogen content steaming accounts for map nitrogen content
The thermal decomposition product for 23.1% for the example.
Embodiment 4
Take appropriate map to be placed in pyrolysis adsorption column, control 100 DEG C of pyrolysis temperature, pyrolysis time 2h, ventilation/quality is
2.4 m3·h-1·kg-1, quality/contact area be 2.17 kg m-2, obtain the ratio that the ammonia-nitrogen content steaming accounts for map nitrogen content
The thermal decomposition product for 12.5% for the example.
Embodiment 5
Take appropriate map to be placed in pyrolysis adsorption column, control 100 DEG C of pyrolysis temperature, pyrolysis time 1h, ventilation/quality is
2.4 m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, obtain the ratio that the ammonia-nitrogen content steaming accounts for map nitrogen content
The thermal decomposition product for 2.3% for the example.
Embodiment 6
Take appropriate map to be placed in pyrolysis adsorption column, control 100 DEG C of pyrolysis temperature, pyrolysis time 3h, ventilation/quality is
2.4 m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, obtain the ratio that the ammonia-nitrogen content steaming accounts for map nitrogen content
The thermal decomposition product for 31.0% for the example.
Embodiment 7
Take appropriate map to be placed in pyrolysis adsorption column, control 100 DEG C of pyrolysis temperature, pyrolysis time 2h, ventilation/quality is
9.6m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, obtain the ratio that the ammonia-nitrogen content steaming accounts for map nitrogen content
The thermal decomposition product for 28.1% for the example.
Embodiment 8
Take appropriate map to be placed in pyrolysis adsorption column, control 100 DEG C of pyrolysis temperature, pyrolysis time 2h, ventilation/quality is
2.4m3·h-1·kg-1, quality/contact area be 1.56kg m-2, obtain the ratio that the ammonia-nitrogen content steaming accounts for map nitrogen content
Thermal decomposition product for 18.3%.
Embodiment 9
Take appropriate map to be placed in pyrolysis adsorption column, control 100 DEG C of pyrolysis temperature, pyrolysis time 2h, ventilation/quality is
1.2m3·h-1·kg-1, quality/contact area be 0.78kg m-2, obtain the ratio that the ammonia-nitrogen content steaming accounts for map nitrogen content
Thermal decomposition product for 3.2%.
Embodiment 10
Map about 6.2g(1bv=10ml in Example 1) it is placed in pyrolysis adsorption column, control 100 DEG C of pyrolysis temperature, pyrolysis
Time 2h, ventilation/quality is 2.4 m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, the ammonia nitrogen amount of removing
For 66.4mg.
Pretreated anaerobic digestion solution in Example 1, is adjusted after pretreatment with the sodium hydroxide solution of 4.0mol/l
Anaerobic digestion solution ph be 8.0, obtain upper prop anaerobic digestion solution, with the flow velocity of 2bv/h carry out drop streaming run absorption upper prop
With ammonia nitrogen in anaerobic digestion solution, it is continuously replenished the sodium hydroxide solution of 0.2mol/l by diluted alkaline fluid supply pump, collect effluent.
The cod mean concentration recording effluent is 154.6mg/l；nh4 +The mean concentration of-n is 5.5mg/l；The mean concentration of sop is
378.6mg/l；The mean concentration of magnesium ion is 520.5mg/l.
Embodiment 11
Map about 6.2g(1bv=10ml in Example 1) it is placed in pyrolysis adsorption column, control 100 DEG C of pyrolysis temperature, pyrolysis
Time 2h, ventilation/quality is 2.4 m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, the ammonia nitrogen amount of removing
For 67.0mg.
Pretreated anaerobic digestion solution in Example 1, is adjusted after pretreatment with the sodium hydroxide solution of 4.0mol/l
Anaerobic digestion solution ph be 9.0, obtain upper prop anaerobic digestion solution, with the flow velocity of 2bv/h carry out drop streaming run absorption upper prop
With ammonia nitrogen in anaerobic digestion solution, it is continuously replenished the sodium hydroxide solution of 0.2mol/l by diluted alkaline fluid supply pump, collect effluent.
The cod mean concentration recording effluent is 174.1mg/l；nh4 +The mean concentration of-n is 6.4mg/l；The mean concentration of sop is
205.1mg/l；The mean concentration of magnesium ion is 293.7mg/l.
Embodiment 12
Map about 6.2g(1bv=10ml in Example 1) it is placed in pyrolysis adsorption column, control 100 DEG C of pyrolysis temperature, pyrolysis
Time 2h, ventilation/quality is 2.4 m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, the ammonia nitrogen amount of removing
For 71.0mg.
Pretreated anaerobic digestion solution in Example 1, is adjusted after pretreatment with the sodium hydroxide solution of 4.0mol/l
Anaerobic digestion solution ph be 9.5, obtain upper prop anaerobic digestion solution, with the flow velocity of 5bv/h carry out drop streaming run absorption upper prop
With ammonia nitrogen in anaerobic digestion solution, it is continuously replenished the sodium hydroxide solution of 0.2mol/l by diluted alkaline fluid supply pump, collect effluent.
The cod mean concentration recording effluent is 145.5mg/l；nh4 +The mean concentration of-n is 7.9mg/l；The mean concentration of sop is
95.7mg/l；The mean concentration of magnesium ion is 127.0mg/l.
Embodiment 13
Map about 6.2g(1bv=10ml in Example 1) it is placed in pyrolysis adsorption column, control 100 DEG C of pyrolysis temperature, pyrolysis
Time 2h, ventilation/quality is 2.4 m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, the ammonia nitrogen amount of removing
For 66.8mg.
Pretreated anaerobic digestion solution in Example 1, is adjusted after pretreatment with the sodium hydroxide solution of 4.0mol/l
Anaerobic digestion solution ph be 10.0, obtain upper prop anaerobic digestion solution, with the flow velocity of 2bv/h carry out drop streaming run absorption upper prop
With ammonia nitrogen in anaerobic digestion solution, it is continuously replenished the sodium hydroxide solution of 0.2mol/l by diluted alkaline fluid supply pump, collect effluent.
The cod mean concentration recording effluent is 154.4mg/l；nh4 +The mean concentration of-n is 1.0mg/l；The mean concentration of sop is
202.1mg/l；The mean concentration of magnesium ion is 239.9mg/l.
Embodiment 14
Map about 6.2g(1bv=10ml in Example 1) it is placed in pyrolysis adsorption column, control 100 DEG C of pyrolysis temperature, pyrolysis
Time 2h, ventilation/quality is 2.4 m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, the ammonia nitrogen amount of removing
For 66.8mg.
Pretreated anaerobic digestion solution in Example 1, is adjusted after pretreatment with the sodium hydroxide solution of 4.0mol/l
Anaerobic digestion solution ph be 9.5, obtain upper prop anaerobic digestion solution, with the flow velocity of 1bv/h carry out drop streaming run absorption upper prop
With ammonia nitrogen in anaerobic digestion solution, it is continuously replenished the sodium hydroxide solution of 0.2mol/l by diluted alkaline fluid supply pump, collect effluent.
The cod mean concentration recording effluent is 160.2mg/l；nh4 +The mean concentration of-n is 0.6mg/l；The mean concentration of sop is
124.3mg/l；The mean concentration of magnesium ion is 192.5mg/l.
Embodiment 15
Measure the effluent property after ammonia nitrogen absorption: nh4 +- n concentration is 12.8mg/l, and the concentration of sop is 227.0mg/l,
The concentration of magnesium ion is 170.3mg/l.
By reaction phosphorus nitrogen mol ratio 1.0: 1, pretreated anaerobic digestion solution is added in obtained effluent, obtains
Mixed liquor；Add part mgcl by reaction magnesium nitrogen mol ratio 2.0: 12Solution is in mixed liquor；Molten with 4.0mol/l sodium hydroxide
Hydraulic control system reaction ph is 8.0, reacts 30min, obtain precipitate and supernatant under 200rpm rotating speed；The nh of supernatant4 +- n is dense
Spend for 34.7mg/l, nh in mixed liquor4 +The response rate of-n is 50.2%；The concentration of sop is 93.7mg/l, and in mixed liquor, sop's returns
Yield is 40.2%.
Precipitate after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Through analysis measure, fresh feed phosphorous
Rate 26.4%, Nitrogen content is 4.6%, and rate containing magnesium is 21.9%, and in fresh feed, magnesium hydroxide seldom, is practically free of organic matter and weight
Metal.
Embodiment 16
Pretreated anaerobic digestion solution is added by the mixed liquor in Example 15 by reaction phosphorus nitrogen mol ratio 1.0: 1
To in the effluent being obtained, obtain mixed liquor；Add part mgcl by reaction magnesium nitrogen mol ratio 2.0: 12Solution is in mixed liquor；
With 4.0mol/l sodium hydroxide solution control reaction ph be 10.0, under 200rpm rotating speed react 30min, obtain precipitate and on
Clear liquid；The nh of supernatant4 +- n concentration is 29.3mg/l, nh in mixed liquor4 +The response rate of-n is 82.2%；The concentration of sop is
0mg/l, in mixed liquor, the response rate of sop is 100%.
Precipitate after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Through analysis measure, fresh feed phosphorous
Rate is 37.9%, and Nitrogen content is 4.2%, and rate containing magnesium is 18.4%, in fresh feed magnesium hydroxide seldom, be practically free of organic matter and
Heavy metal.
Embodiment 17
Pretreated anaerobic digestion solution is added by the mixed liquor in Example 15 by reaction phosphorus nitrogen mol ratio 1.2: 1
To in the effluent being obtained, obtain mixed liquor；Add part mgcl by reaction magnesium nitrogen mol ratio 2.0: 12Solution is in mixed liquor；
With 4.0mol/l sodium hydroxide solution control reaction ph be 9.0, under 200rpm rotating speed react 30min, obtain precipitate and on
Clear liquid；The nh of supernatant4 +- n concentration is 27.4mg/l, nh in mixed liquor4 +The response rate of-n is 55.7%；The concentration of sop is
80.5mg/l, in mixed liquor, the response rate of sop is 51.1%.
Precipitate after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Through analysis measure, fresh feed phosphorous
Rate is 27.9%, and Nitrogen content is 4.9%, and rate containing magnesium is 18.2%, in fresh feed magnesium hydroxide seldom, be practically free of organic matter and
Heavy metal.
Embodiment 18
Pretreated anaerobic digestion solution is added by the mixed liquor in Example 15 by reaction phosphorus nitrogen mol ratio 0.8: 1
To in the effluent being obtained, obtain mixed liquor；Add part mgcl by reaction magnesium nitrogen mol ratio 2.0: 12Solution is in mixed liquor；
With 4.0mol/l sodium hydroxide solution control reaction ph be 9.0, under 200rpm rotating speed react 30min, obtain precipitate and on
Clear liquid；The nh of supernatant4 +- n concentration is 21.9mg/l, nh in mixed liquor4 +The response rate of-n is 72.5%；The concentration of sop is
6.0mg/l, in mixed liquor, the response rate of sop is 95.9%.
Precipitate after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Through analysis measure, fresh feed phosphorous
Rate is 23.5%, and Nitrogen content is 4.9%, and rate containing magnesium is 18.6%, in fresh feed magnesium hydroxide seldom, be practically free of organic matter and
Heavy metal.
Embodiment 19
Pretreated anaerobic digestion solution is added by the mixed liquor in Example 15 by reaction phosphorus nitrogen mol ratio 1.0: 1
To in the effluent being obtained, obtain mixed liquor；Add part mgcl by reaction magnesium nitrogen mol ratio 1.5: 12Solution is in mixed liquor；
With 4.0mol/l sodium hydroxide solution control reaction ph be 9.0, under 200rpm rotating speed react 30min, obtain precipitate and on
Clear liquid；The nh of supernatant4 +- n concentration is 25.6mg/l, nh in mixed liquor4 +The response rate of-n is 63.3%；The concentration of sop is
6.0mg/l, in mixed liquor, the response rate of sop is 96.2%.
Precipitate after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Through analysis measure, fresh feed phosphorous
Rate is 28.6%, and Nitrogen content is 5.8%, and rate containing magnesium is 17.4%, in fresh feed magnesium hydroxide seldom, be practically free of organic matter and
Heavy metal.
Embodiment 20
Pretreated anaerobic digestion solution is added by the mixed liquor in Example 15 by reaction phosphorus nitrogen mol ratio 1.0: 1
To in the effluent being obtained, obtain mixed liquor；Add part mgcl by reaction magnesium nitrogen mol ratio 1.8: 12Solution is in mixed liquor；
With 4.0mol/l sodium hydroxide solution control reaction ph be 9.0, under 200rpm rotating speed react 30min, obtain precipitate and on
Clear liquid；The nh of supernatant4 +- n concentration is 0mg/l, nh in mixed liquor4 +The response rate of-n is 100%；The concentration of sop is 12.0mg/
L, in mixed liquor, the response rate of sop is 92.3%.
Precipitate after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Through analysis measure, fresh feed phosphorous
Rate is 26.8%, and Nitrogen content is 6.2%, and rate containing magnesium is 17.4%, in fresh feed magnesium hydroxide seldom, be practically free of organic matter and
Heavy metal.
Embodiment 21
Mixed sediment in Example 1 is pyrolyzed again, controls 100 DEG C of pyrolysis temperature, pyrolysis time 2h, ventilation
Amount/quality is 2.4 m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, the ammonia nitrogen amount of removing is 49.5mg, ammonia
Nitrogen enriching quantity is 115.6mg.
Pretreated anaerobic digestion solution in Example 1, the sodium hydroxide solution with 4.0mol/l is pretreated
Anaerobic digestion solution ph is 10.0, carries out dropping streaming and running adsorbing ammonia nitrogen in upper prop anaerobic digestion solution with the flow velocity of 2bv/h, passes through
Diluted alkaline fluid supply pump is continuously replenished the sodium hydroxide solution of 0.2mol/l, and it is 10.0 that run duration controls adsorption reaction ph, collects
Effluent, obtains product after ammonia nitrogen absorption after the completion of absorption.The cod mean concentration recording effluent is 183.2mg/l；nh4 +-n
Mean concentration be 2.4mg/l；The mean concentration of sop is 232.1mg/l；The mean concentration of magnesium ion is 120.0mg/l；Upper prop
Reach 240ml with anaerobic digestion solution treating capacity.
The phosphorous rate of ammonia nitrogen absorption postprecipitation thing is 38.7%, and Nitrogen content is 6.2%, and rate containing magnesium is 26.0%, is practically free of organic
Matter and heavy metal, are a kind of rich rocks phosphate in powder of function admirable.
By reaction phosphorus nitrogen mol ratio 1.0: 1, pretreated anaerobic digestion solution is added in obtained effluent, obtains
Mixed liquor；Add part mgcl by reaction magnesium nitrogen mol ratio 1.8: 12Solution is in mixed liquor；Molten with 4.0mol/l sodium hydroxide
Hydraulic control system reaction ph is 9.0, reacts 30min, sucking filtration, obtain precipitate and supernatant under 200rpm rotating speed；The nh of supernatant4 +- n concentration is 12.5mg/l, and the concentration of sop is 9.3mg/l.
Precipitate after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Measure through analysis, the phosphorous rate of fresh feed
For 26.8%, Nitrogen content is 6.2%, and rate containing magnesium is 17.5%, and in fresh feed, magnesium hydroxide composition increases, and is practically free of
Machine matter and heavy metal.
Fresh feed is transferred in pyrolysis adsorption column, for next pyrolysis.
Embodiment 22
Take map about 6.2g(1bv=10ml) it is placed in pyrolysis adsorption column, 100 DEG C of pyrolysis temperature of control, pyrolysis time 2h,
Ventilation/quality is 2.4 m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, the ammonia nitrogen amount of removing is
80.1mg.
Pretreated anaerobic digestion solution in Example 1, adjusts pretreatment with the sodium hydroxide solution of 4.0mol/l
Anaerobic digestion solution ph afterwards is 10.0, carries out dropping streaming and running adsorbing ammonia nitrogen in upper prop anaerobic digestion solution with the flow velocity of 2bv/h,
It is continuously replenished the sodium hydroxide solution of 0.2mol/l by diluted alkaline fluid supply pump, it is 10.0 that run duration controls adsorption reaction ph,
Collect effluent, after the completion of absorption, obtain product after ammonia nitrogen absorption.The cod mean concentration recording effluent is 163.5mg/l；
nh4 +The mean concentration of-n is 1.6mg/l；The mean concentration of sop is 163.5mg/l；The mean concentration of magnesium ion is 134.1mg/
l；Upper prop anaerobic digestion solution treating capacity reaches 280ml.
Dry product after ammonia nitrogen absorption at 40 ~ 45 DEG C, measure through analysis, after ammonia nitrogen absorption, the phosphorous rate of product is 26.3%,
Nitrogen content is 5.2%, and rate containing magnesium is 15.4%, and in product after ammonia nitrogen absorption, magnesium hydroxide and magnesium pyrophosphate composition are less, hardly
Containing organic and heavy metal.
After the completion of absorption, it is pyrolyzed again according to pyrolytical condition before, acquisition ammonia nitrogen removal amount is 44.8mg, ammonia nitrogen is enriched with
Measure as 124.9mg.
Pretreated anaerobic digestion solution in Example 1, is adsorbed again according to adsorption conditionses before,
Collect effluent.The cod mean concentration recording effluent is 154.6mg/l；nh4 +The mean concentration of-n is 3.4mg/l；Sop's
Mean concentration is 75.1mg/l；The mean concentration of magnesium ion is 174.0mg/l；Upper prop anaerobic digestion solution treating capacity reaches 240ml.
Measure through analysis, after ammonia nitrogen absorption, the phosphorous rate of product is 24.2%, Nitrogen content is 5.2%, rate containing magnesium is 35.5%, ammonia
In product after N2 adsorption, magnesium hydroxide and magnesium pyrophosphate composition increased, and are practically free of organic matter and heavy metal, are a kind of property
The excellent rich rock phosphate in powder of energy.
Effluent twice is mixed, by reaction phosphorus nitrogen mol ratio 1.0: 1, pretreated anaerobic digestion solution is thrown
Plus in the effluent being obtained；Add part mgcl by reaction magnesium nitrogen mol ratio 1.8: 12Solution is in mixed liquor；Use 4.0mol/l
It is 9.0 that sodium hydroxide solution controls reaction ph, reacts 30min, obtain precipitate and supernatant under 200rpm rotating speed；Supernatant
Nh4 +- n concentration is 17.4mg/l, and the concentration of sop is 11.6mg/l.
Precipitate after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Measure through analysis, the phosphorous rate of fresh feed
For 20.3%, Nitrogen content is 8.7%, and rate containing magnesium is 17.5%, is practically free of organic matter and heavy metal in fresh feed.
Embodiment 23
Starting: take map about 6.2g(1bv=10ml) it is placed in pyrolysis adsorption column, control 100 DEG C of pyrolysis temperature, during pyrolysis
Between 2h, ventilation/quality be 2.4 m3·h-1·kg-1, quality/contact area be 0.78 kg m-2, the ammonia nitrogen amount steaming is
66.1mg.
Pretreated anaerobic digestion solution in Example 1, adjusts pretreatment with the sodium hydroxide solution of 4.0mol/l
Anaerobic digestion solution ph afterwards is 10.0, obtains upper prop anaerobic digestion solution, carries out dropping streaming and running adsorbing with the flow velocity of 2bv/h
Ammonia nitrogen in post anaerobic digestion solution, is continuously replenished the sodium hydroxide solution of 0.2mol/l, run duration by diluted alkaline fluid supply pump
Control adsorption reaction ph to be 10.0, collect effluent.
In effluent, ammonia nitrogen mean concentration thinks that ammonia nitrogen absorption completes when being more than 0.Detection effluent nh4 +- n's is averagely dense
Spend for 1.1 mg/l；The mean concentration of sop is 202.1mg/l；The mean concentration of magnesium ion is 239.9mg/l；Ammonia nitrogen absorption mistake
In journey, anaerobic digestion solution treating capacity reaches 280ml.
After the completion of ammonia nitrogen absorption, product is dried at 40 ~ 45 DEG C, obtains product 5374.3mg after absorption, and its phosphorous rate is
28.6%, Nitrogen content is 8.5%, and rate containing magnesium is 15.6%.
By reaction phosphorus nitrogen mol ratio 1.0: 1, pretreated anaerobic digestion solution 155ml is added in obtained effluent,
Obtain mixed liquor；Add part mgcl by reaction magnesium nitrogen mol ratio 1.8: 12Solution is in mixed liquor；Use 4.0mol/l hydroxide
It is 9.0 that sodium solution controls reaction ph, reacts 30min under 200rpm rotating speed, and the precipitate after filtration is dried at 40 ~ 45 DEG C,
Obtain fresh feed 402.5mg.
Circulation 1: fresh feed is transferred in pyrolysis adsorption column, being pyrolyzed the ammonia nitrogen amount steaming is 49.5mg, is adsorbed
Operation, detects effluent nh4 +The mean concentration of-n is 2.4mg/l；The mean concentration of sop is 67.6mg/l；Magnesium ion average
Concentration is 120.0mg/l；During ammonia nitrogen absorption, upper prop anaerobic digestion solution treating capacity reaches 240ml.Produce after obtaining ammonia nitrogen absorption
Thing 5232.6mg, its phosphorous rate is 40.9%, and Nitrogen content is 8.4%, and rate containing magnesium is 35.3%.Locate in advance in nutrient removal process
Anaerobic digestion solution treating capacity after reason is 52ml, obtains fresh feed 134.6 mg, and its phosphorous rate is 32.9%, and Nitrogen content is
4.6%, rate containing magnesium is 24.3%.
Circulation 2: fresh feed is transferred in pyrolysis adsorption column, being pyrolyzed the ammonia nitrogen amount steaming is 36.7mg, is adsorbed
Operation, detects effluent nh4 +The mean concentration of-n is 6.2mg/l；The mean concentration of sop is 144.8mg/l；Magnesium ion average
Concentration is 76.9mg/l；During ammonia nitrogen absorption, upper prop anaerobic digestion solution treating capacity reaches 160ml.Obtain product after ammonia nitrogen absorption
5195.8mg, its phosphorous rate is 38.7%, and Nitrogen content is 6.2%, and rate containing magnesium is 31.7%.Pretreatment in nutrient removal process
Anaerobic digestion solution treating capacity afterwards is 79ml, obtains fresh feed 206.0 mg, and its phosphorous rate is 34.8%, and Nitrogen content is 4.6%,
Rate containing magnesium is 25.0%.
Circulation 3: fresh feed is transferred in pyrolysis adsorption column, being pyrolyzed the ammonia nitrogen amount steaming is 29.1mg, is adsorbed
Operation, detects effluent nh4 +The mean concentration of-n is 9.1mg/l；The mean concentration of sop is 77.3mg/l；Magnesium ion average
Concentration is 36.9mg/l；During ammonia nitrogen absorption, upper prop anaerobic digestion solution treating capacity reaches 160ml.Obtain product after ammonia nitrogen absorption
5009.7mg, its phosphorous rate is 36.3%, and Nitrogen content is 5.5%, and rate containing magnesium is 27.6%.Pretreatment in nutrient removal process
Anaerobic digestion solution treating capacity afterwards is 42ml, obtains fresh feed 110.0 mg, and its phosphorous rate is 31.2%, and Nitrogen content is 5.3%,
Rate containing magnesium is 29.1%.
Circulation 4: fresh feed is transferred in pyrolysis adsorption column, being pyrolyzed the ammonia nitrogen amount steaming is 22.8mg, is adsorbed
Operation, detects effluent nh4 +The mean concentration of-n is 9.1mg/l；The mean concentration of sop is 66.0mg/l；Magnesium ion average
Concentration is 72.5mg/l；During ammonia nitrogen absorption, upper prop anaerobic digestion solution treating capacity reaches 160ml.Obtain product after ammonia nitrogen absorption
4901.6mg, its phosphorous rate is 38.6%, and Nitrogen content is 5.6%, and rate containing magnesium is 31.0%.Pretreatment in nutrient removal process
Anaerobic digestion solution treating capacity afterwards is 37ml, obtains fresh feed 94.8mg, and its phosphorous rate is 32.4%, and Nitrogen content is 6.5%, contains
Magnesium rate is 43.5%.
Circulation 5: fresh feed is transferred in pyrolysis adsorption column, being pyrolyzed the ammonia nitrogen amount steaming is 19.5mg, is adsorbed
Operation, detects effluent nh4 +The mean concentration of-n is 10.2mg/l；The mean concentration of sop is 48.8mg/l；Magnesium ion average
Concentration is 64.3mg/l；During ammonia nitrogen absorption, upper prop anaerobic digestion solution treating capacity reaches 120ml.Obtain product after ammonia nitrogen absorption
4848.9mg, its phosphorous rate is 37.2%, and Nitrogen content is 9.3%, and rate containing magnesium is 31.4%.Pretreatment in nutrient removal process
Anaerobic digestion solution treating capacity afterwards is 27ml, obtains fresh feed 69.4mg, and its phosphorous rate is 34.4%, and Nitrogen content is 5.8%, contains
Magnesium rate is 31.5%.
Circulation 6: fresh feed is transferred in pyrolysis adsorption column, being pyrolyzed the ammonia nitrogen amount steaming is 18.4mg, is adsorbed
Operation, detects effluent nh4 +The mean concentration of-n is 11.9mg/l；The mean concentration of sop is 31.5mg/l；Magnesium ion average
Concentration is 39.8mg/l；During ammonia nitrogen absorption, upper prop anaerobic digestion solution treating capacity reaches 120ml.Obtain product after ammonia nitrogen absorption
4737.8mg, its phosphorous rate is 35.6%, and Nitrogen content is 10.0%, and rate containing magnesium is 31.6%.Pretreatment in nutrient removal process
Anaerobic digestion solution treating capacity afterwards is 14ml, obtains fresh feed 35.9mg, and its phosphorous rate is 34.9%, and Nitrogen content is 5.4%, contains
Magnesium rate is 34.7%.
Circulation 7: fresh feed is transferred in pyrolysis adsorption column, being pyrolyzed the ammonia nitrogen amount steaming is 15.7mg.Illustrate to be pyrolyzed
In adsorption column, mixture still has pyrolysis again, absorption ammonia nitrogen and the potentiality reclaiming nitrogen phosphorus.
Take turns cyclic test through 7, in pyrolysis adsorption column, material still has 4918.3mg, can discharge as rich rock phosphate in powder, and has
There is good ammonia nitrogen absorption performance it is also possible to be continuing with as ammonia nitrogen adsorbent, the TAN steaming is 257.8mg, ammonia
In nitrogen adsorption process, upper prop anaerobic digestion solution process total amount reaches 1240ml, pretreated anaerobism in nutrient removal process
It is 406ml that Digestive system processes total amount, and coprocessing anaerobic digestion solution total amount reaches 1646ml.
Fresh feed used above is the prepared precipitate of circulation raw material after drying.
Claims (9)
1. a kind of reclaim urban mud anaerobic digestion solution in nitrogen phosphorus method it is characterised in that: pyrolysis adsorption column in, first right
Map carries out pyrolysis and obtains absorption material, reclaims the ammonia that pyrolysis is discharged；Then pass to upper prop anaerobic digestion solution to carry out at absorption
Reason, obtains effluent；Ammonia nitrogen concentration in detection effluent, when ammonia nitrogen concentration is more than 0, stops absorption, first supplements fresh former
Material, then be pyrolyzed, reclaim the ammonia that pyrolysis is discharged, then proceed to absorption, detection is circulated operation；Wherein, fresh feed
It is to add mgcl in the mixed liquor with pretreated anaerobic digestion solution for the effluent2The precipitate that solution is obtained is after drying
Raw material；In the ammonia reclaiming and final pyrolysis adsorption column, material is recovery of nitrogen and phosphorus product；Comprise the following steps:
(1) urban mud anaerobic digestion solution is filtered, obtain anaerobic digestion solution after filter, then adjust anaerobism after filter with hydrochloric acid and disappear
Change liquid ph to 3.5～4.0, obtain pretreated anaerobic digestion solution；Adjust pretreated anaerobism with sodium hydroxide solution to disappear
The ph changing liquid is 8.0～10.0, obtains upper prop anaerobic digestion solution；
(2) pyrolysis temperature is controlled to be 80～100 DEG C, pyrolysis time 1～3h, ventilation/quality is 1.2～9.6m3·h-1·kg-1, quality/contact area be 0.78～2.17kg m-2, in pyrolysis adsorption column, map is pyrolyzed, the ammonia steaming is by filling
The absorption bottle having dilute sulfuric acid absorbs；
(3) upper prop anaerobic digestion solution is passed through pyrolysis adsorption column, carries out dropping streaming operation, runtime with the flow velocity of 1～5bv/h
Between to control adsorption reaction ph with sodium hydroxide solution be 8.0～10.0, obtain product collect effluent after ammonia nitrogen absorption；
(4) press reaction phosphorus nitrogen mol ratio to add after the pretreatment in step (1) of effluent in step (3) for 0.8～1.2: 1
Anaerobic digestion solution in, obtain mixed liquor；Add mgcl by reaction magnesium nitrogen mol ratio for 1.5～2.0: 12Solution is to mixed liquor
In；With sodium hydroxide solution control reaction ph be 7.0～10.0, under 200rpm rotating speed react 30min, obtain precipitate and on
Clear liquid；
(5) press the continuous absorption of step (3), the ammonia nitrogen concentration in detection effluent, when ammonia nitrogen concentration is more than 0, stop absorption；
(6) dry precipitate, obtain fresh feed；First transfer fresh raw material is in pyrolysis adsorption column, then presses step (2)～(5)
It is circulated operation；In the ammonia reclaiming and final pyrolysis adsorption column, material is recovery of nitrogen and phosphorus product.
2. according to claim 1 reclaim urban mud anaerobic digestion solution in nitrogen phosphorus method it is characterised in that: step
(1), in, the composite fibre membrane filtration being 0.45 μm using aperture removes float and part in urban mud anaerobic digestion solution
Organic.
3. according to claim 1 reclaim urban mud anaerobic digestion solution in nitrogen phosphorus method it is characterised in that: step
(1), in, adjusting anaerobic digestion solution ph after filter using the hydrochloric acid for 2.0mol/l for the concentration is 4.0；Using concentration for 4.0mol/l's
The ph that sodium hydroxide solution adjusts pretreated anaerobic digestion solution is 10.0.
4. according to claim 1 reclaim urban mud anaerobic digestion solution in nitrogen phosphorus method it is characterised in that: step
(3), in, controlling adsorption reaction ph using the sodium hydroxide solution for 0.2mol/l for the concentration is 10.0；After ammonia nitrogen absorption, product is nitrogenous
Rate is with nh4 +- n is calculated as 4～10%, and phosphorous rate is with p2o5It is calculated as 24～41%, rate containing magnesium is calculated as 15～36% with mgo.
5. according to claim 1 reclaim urban mud anaerobic digestion solution in nitrogen phosphorus method it is characterised in that: step
(4), in, controlling reaction ph using the sodium hydroxide solution for 4.0mol/l for the concentration is 9.0.
6. according to claim 1 reclaim urban mud anaerobic digestion solution in nitrogen phosphorus method it is characterised in that: step
(4) in, reaction phosphorus nitrogen mol ratio is 1.0～1.1: 1, and reaction magnesium nitrogen mol ratio is 1.8～2.0: 1, and reaction ph is 9.0.
7. according to claim 1 reclaim urban mud anaerobic digestion solution in nitrogen phosphorus method it is characterised in that: step
(4), in, in mixed liquor, the response rate of nitrogen and phosphorus respectively reaches 91% and more than 92%；Fresh feed Nitrogen content is with nh4 +- n counts
For 4～9%, phosphorous rate is with p2o5It is calculated as 20～38%, rate containing magnesium is calculated as 17～44% with mgo.
8. according to claim 1 reclaim urban mud anaerobic digestion solution in nitrogen phosphorus method it is characterised in that: step
(6), in, dry sedimentary temperature and be 40～45 DEG C.
9. the special purpose device reclaiming the method for nitrogen phosphorus in urban mud anaerobic digestion solution according to claim 1, its feature
It is: include thermostatic water-circulator bath pot (1), thermal plume of air (2), pyrolysis adsorption column (3), air pump (4), desiccant (6), absorption bottle
(7), upper prop anaerobic digestion liquid storage tank (8), pretreated anaerobic digestion liquid storage tank (18), diluted alkaline flow container (11), mgcl2Molten
Liquid storage tank (21), concentrated base flow container (24), nutrient reclaim retort (15), the electrode probe (17) of ph meter (16), ph meter, go out
Hopper (30)；Described thermostatic water-circulator bath pot (1) is connected with thermal plume of air (2), and described thermal plume of air (2) is adsorbed with pyrolysis
Post (3) is connected, and described air pump (4), glass rotameter (5) are connected with thermal plume of air (2), in pyrolysis adsorption column (3)
If desiccant (6), described absorption bottle (7) is connected with pyrolysis adsorption column (3), and described upper prop is with anaerobic digestion liquid storage tank (8)
Be connected with pyrolysis adsorption column (3), the electrode probe that described pyrolysis adsorption column (3) effluent, concentrated base flow container (24), ph count
(17), pretreated anaerobic digestion liquid storage tank (18) and mgcl2Solution reservoir (21) all reclaims retort with nutrient
(15) it is connected；Described diluted alkaline flow container (11) is connected with pyrolysis adsorption column (3).
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004174332A (en) * | 2002-11-26 | 2004-06-24 | Kubota Corp | Method for treating waste water containing phosphoric acid and ammonia |
| CN101555076A (en) * | 2008-04-11 | 2009-10-14 | 中国科学院广州地球化学研究所 | Ammonian remover used for treating highly concentrated ammonian wastewater and treatment method |
| CN102267755A (en) * | 2011-07-22 | 2011-12-07 | 中国矿业大学(北京) | Pretreatment and reclaiming method for ammonia nitrogen in acrylic fiber wastewater |
| CN102336504A (en) * | 2011-09-05 | 2012-02-01 | 同济大学 | Struvite circulating crystallization method for treating synthetic ammonia wastewater |
| CN102674523A (en) * | 2012-05-24 | 2012-09-19 | 南京大学 | Method for recycling ammonia and nitrogen in waste watery by aid of chemicrystallization |
| CN103466829A (en) * | 2013-08-30 | 2013-12-25 | 常州大学 | Treatment method of high-concentration ammonia nitrogen waste water and treatment system of treatment method |
-
2015
- 2015-07-16 CN CN201510417785.7A patent/CN105060542B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004174332A (en) * | 2002-11-26 | 2004-06-24 | Kubota Corp | Method for treating waste water containing phosphoric acid and ammonia |
| CN101555076A (en) * | 2008-04-11 | 2009-10-14 | 中国科学院广州地球化学研究所 | Ammonian remover used for treating highly concentrated ammonian wastewater and treatment method |
| CN102267755A (en) * | 2011-07-22 | 2011-12-07 | 中国矿业大学(北京) | Pretreatment and reclaiming method for ammonia nitrogen in acrylic fiber wastewater |
| CN102336504A (en) * | 2011-09-05 | 2012-02-01 | 同济大学 | Struvite circulating crystallization method for treating synthetic ammonia wastewater |
| CN102674523A (en) * | 2012-05-24 | 2012-09-19 | 南京大学 | Method for recycling ammonia and nitrogen in waste watery by aid of chemicrystallization |
| CN103466829A (en) * | 2013-08-30 | 2013-12-25 | 常州大学 | Treatment method of high-concentration ammonia nitrogen waste water and treatment system of treatment method |
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Application publication date: 20151118 Assignee: Zhenjiangnan Zhimo Technology Co.,Ltd. Assignor: NANJING FORESTRY University Contract record no.: X2021980008139 Denomination of invention: The invention relates to a method for recovering nitrogen and phosphorus from anaerobic digestion liquid of municipal sludge and a special device thereof Granted publication date: 20170118 License type: Common License Record date: 20210823 |
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Application publication date: 20151118 Assignee: Nanjing xinbud Environmental Engineering Co.,Ltd. Assignor: NANJING FORESTRY University Contract record no.: X2021980008256 Denomination of invention: The invention relates to a method for recovering nitrogen and phosphorus from anaerobic digestion liquid of municipal sludge and a special device thereof Granted publication date: 20170118 License type: Common License Record date: 20210824 Application publication date: 20151118 Assignee: Nanjing Chunsheng Environmental Technology Co.,Ltd. Assignor: NANJING FORESTRY University Contract record no.: X2021980008369 Denomination of invention: The invention relates to a method for recovering nitrogen and phosphorus from anaerobic digestion liquid of municipal sludge and a special device thereof Granted publication date: 20170118 License type: Common License Record date: 20210825 |