CN105060542A - 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, relate to process and its recovery method as resource of urban mud anaerobic digestion solution, be specifically related to a kind of method and the special purpose device thereof that reclaim nitrogen phosphorus in urban mud anaerobic digestion solution.
Background technology
" 12 " period, China implements overall control by the ammonia nitrogen discharge in key industry and key area, and first ammonia nitrogen is included in the binding indicator system reinforcement supervision, explicitly calls for reduction of discharging 10%.According to 2013 " China Environmental State Bulletin " statistics, inorganic nitrogen and reactive phosphate are classified as main contamination index by the whole nation four large sea area immediate offshore areas; 423 daily blowdown water amounts in the whole nation are greater than the in line extra large industrial pollution source of 100 cubic metres, ammonia nitrogen total emission volumn is 1.69 ten thousand tons in domestic pollution source and comprehensive sewage draining exit, and total phosphorus total emission volumn is 2841 tons.A large amount of nitrogen phosphorus enters in water body, not only pollutes environment, wastes a large amount of precious resources simultaneously.
The meaning reclaiming nitrogen phosphorus from sewage is: (1) reduces nitrogen phosphorus to discharge into water, prevents body eutrophication; (2) in sewage, nitrogen phosphorus reclaims the load that effectively can reduce sewage work's process nitrogen phosphorus, reduces the processing cost of sewage, improves treatment effect; (3) recovery product can be the nitrogen phosphorus raw material that industrial production provides new, has saved nitrogen phosphor resource, has met the requirement of nitrogen phosphor resource sustainable use; (4) some nitrogen phosphorus recovery product has certain market potential value, can be directly used in slow-release fertilizer etc.
The processing method research of reclaiming nitrogen phosphorus at present from sewage is more, comprises the precipitator method, crystallization process, absorption method, ion exchange method etc.These methods or because of the rate of recovery not high, or it is low to reclaim product qualities, or recovery process is complicated and cost recovery is higher and fail to be widely used.
Liu Dapengs etc. utilize MAP method to add Na
2hPO
412H
2o and MgCl
26H
2o removes the ammonia nitrogen in high density in coking chemical waste water, works as n(Mg
2+): n(NH
4 +): n(PO
4 3-) be 1.3: 1: 0.9, under the condition of optimal ph 8.5 ~ 10.0, NH
4 +-N clearance is more than 96%, and remaining phosphorus mass concentration is lower than 20mg/L; Zhang Yanyan etc. utilize natural pond, MAP method treatment of simulated pig farm liquid, and the mass concentration of ammonia nitrogen is 350 ~ 750mg/L, and the mass concentration of soluble phosphate is 55mg/L, according to n(Mg): n(P)=1.5 add MgCl
2, when reacting pH=10, tp removal rate up to 97%, ammonia nitrogen removal frank only 20%; Li Shisong etc. based on MAP method seawater coagulation process Nitrogen-and Phosphorus-containing waste water, to NH
4 +the nitrogen phosphorus waste water that-N starting point concentration is respectively 115.69mg/L, 274.41mg/L, 505.69mg/L processes, by adding NaH
2pO
4control N: P mol ratio is 1: 1, by the pH value to 9.5 of sodium hydroxide solution and HCl regulator solution, works as NH
4 +when the purity of-N clearance and MAP is the highest, NH
4 +-N clearance is 68.32 ~ 73.35%; Xiang Xuemin etc. adopt hot acid combined method lignin-sludge to discharge phosphorus, and add ammonium chloride using seawater as magnesium source simultaneously and reclaim phosphorus in rich phosphorus supernatant liquor with magnesium ammonium phosphate form, and positive phosphorous recovery can reach 94.89%; Phosphorus in sludge dewatering supernatant liquor and nitrogen are reclaimed in the research such as Battistoni using seawater as magnesium source, do not need to add chemical agent, the soluble phosphate of about 70% can precipitate recovery; Korchef etc. have studied Mg
2+, PO
4 3-, NH
4 +reclaim the effect in phosphorus process at magnesium ammonium phosphate, find NH
4 +when concentration is increased to 227.27mg/L by 18.92mg/L, phosphorous recovery increases to 75% by 21%; Jaffer etc. are to when finding that pH9.0, Mg/P mol ratio is 1.05 in the pilot plant test of the waste water reclamation phosphorus of phosphorus concentration 167mg/L, and phosphorous recovery can reach 97%.
In sum, mainly there is some problem following in the above method based on the process of MAP method and recovery nitrogen phosphorus: when (1) is not using seawater as magnesium source, magnesium salts dosage is large, and reagent cost is high; (2), time using seawater as magnesium source, supplementary phosphorus source is often needed, meanwhile, due to K
+, Ca
2+and Mg
2+introducing, the purity reclaiming product can corresponding decline; (3) when reclaiming nitrogen phosphorus the same period, often can not obtain higher nitrogen phosphorous recovery simultaneously; (4) phosphor resource reclaimed fails to reuse in follow-up nitrogen phosphorus reclaims.Therefore, how while reduction medicament expense, improve the problems such as the phosphor resource that nitrogen phosphorous recovery and recycle reclaim and become the study hotspot that nitrogen phosphorus reclaims.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of this invention is to provide a kind of method reclaiming nitrogen phosphorus in urban mud anaerobic digestion solution, utilize the characteristic of MAP and pyrolysis product thereof from urban mud anaerobic digestion solution, to reclaim nitrogen phosphor resource and recycle.Another object of the present invention is to provide the special purpose device of the method for nitrogen phosphorus in a kind of above-mentioned recovery urban mud anaerobic digestion solution.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is:
A kind of method reclaiming nitrogen phosphorus in urban mud anaerobic digestion solution: in thermal desorption attached column, first to MAP(MgNH
4pO
46H
2o) carry out pyrolysis and obtain absorption material, reclaim the ammonia that pyrolysis is discharged; Then pass into upper prop anaerobic digestion solution and carry out adsorption treatment, obtain effluent liquid; Detect the ammonia nitrogen concentration in effluent liquid, when ammonia nitrogen concentration is greater than 0, stop absorption, first supplement fresh feed, then carry out pyrolysis, reclaim the ammonia that pyrolysis is discharged, then continue absorption, detect and carry out cyclical operation; Wherein, fresh feed is add MgCl in the mixed solution of effluent liquid and pretreated anaerobic digestion solution
2the throw out that solution obtains raw material after drying; Reclaim ammonia and final thermal desorption attached column in material be nitrogen phosphorus reclaim product.
The method of nitrogen phosphorus in described recovery urban mud anaerobic digestion solution, comprises the following steps:
(1) urban mud anaerobic digestion solution is filtered, obtain the rear anaerobic digestion solution of filter, then with anaerobic digestion solution pH to 3.5 ~ 4.0 after hydrochloric acid adjustment filter, obtain pretreated anaerobic digestion solution; Regulate the pH of pretreated anaerobic digestion solution to be 8.0 ~ 10.0 with sodium hydroxide solution, obtain upper prop anaerobic digestion solution;
(2) controlling pyrolysis temperature is 80 ~ 100 DEG C, and pyrolysis time 1 ~ 3h, air flow/quality is 1.2 ~ 9.6m
3h
-1kg
-1, quality/contact area is 0.78 ~ 2.17kgm
-2, in thermal desorption attached column, carry out pyrolysis to MAP, the ammonia steamed is absorbed by the absorption bottle that dilute sulphuric acid is housed;
(3) upper prop anaerobic digestion solution is passed into thermal desorption attached column, carry out falling streaming with the flow velocity of 1 ~ 5BV/h and run, it is 8.0 ~ 10.0 that run duration sodium hydroxide solution controls absorption reaction pH, obtains ammonia nitrogen absorption after product and collects effluent liquid;
(4) be add effluent liquid in step (3) in pretreated anaerobic digestion solution in step (1), acquisition mixed solution at 0.8 ~ 1.2: 1 by reaction phosphorus nitrogen mol ratio; Be add MgCl at 1.5 ~ 2.0: 1 by reaction magnesium nitrogen mol ratio
2solution is in mixed solution; Controlling reaction pH with sodium hydroxide solution is 7.0 ~ 10.0, under 200rpm rotating speed, react 30min, obtains throw out and supernatant liquor;
(5) by step (3) continuous adsorption, detect the ammonia nitrogen concentration in effluent liquid, when ammonia nitrogen concentration is greater than 0, stop absorption;
(6) dry throw out, obtain fresh feed; First transfer fresh raw material in thermal desorption attached column, then carries out cyclical operation by step (2) ~ (5); Reclaim ammonia and final thermal desorption attached column in material be nitrogen phosphorus reclaim product.
In step (1), aperture is adopted to be suspended substance and part organic matter in the blend fiber membrane filtration removal urban mud anaerobic digestion solution of 0.45 μm.
In step (1), concentration is adopted to be that after the hydrochloric acid adjustment filter of 2.0mol/L, anaerobic digestion solution pH is 4.0; Employing concentration is that the sodium hydroxide solution of 0.2mol/L regulates the pH of pretreated anaerobic digestion solution to be 10.0.
In step (3), employing concentration is the sodium hydroxide solution control absorption reaction pH of 0.2mol/L is 10.0; Ammonia nitrogen absorption after product Nitrogen content is with NH
4 +-N counts 4 ~ 10%, and phosphorous rate is with P
2o
5count 24 ~ 41%, count 15 ~ 36% containing magnesium rate with MgO.
In step (4), employing concentration is the sodium hydroxide solution control reaction pH of 4.0mol/L 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, and reaction pH is 9.0.
In step (4), in mixed solution, the rate of recovery of nitrogen and phosphorus can reach more than 91% and 92% respectively; Fresh feed Nitrogen content is with NH
4 +-N counts 4 ~ 9%, and phosphorous rate is with P
2o
5count 20 ~ 38%, count 17 ~ 44% containing magnesium rate with MgO.
In step (6), drying sedimentary temperature is 40 ~ 45 DEG C.
The special purpose device of the method for nitrogen phosphorus in described recovery urban mud anaerobic digestion solution, comprises thermostatic water-circulator bath pot (1), thermal plume of air (2), thermal desorption attached column (3), air pump (4), siccative (6), absorption bottle (7), upper prop anaerobic digestion liquid storage tank (8), pretreated anaerobic digestion liquid storage tank (18), diluted alkaline flow container (11), MgCl
2solution reservoir (21), concentrated base flow container (24), nutritive element reclaim retort (15), pH meter (16), the electrode probe (17) of pH meter, feed box (30), described thermostatic water-circulator bath pot (1) is connected with thermal plume of air (2), described thermal plume of air (2) is connected with thermal desorption attached column (3), described air pump (4), glass rotameter (5) is connected with thermal plume of air (2), siccative (6) is established in thermal desorption attached column (3), described absorption bottle (7) is connected with thermal desorption attached column (3), described upper prop anaerobic digestion liquid storage tank (8) is connected with thermal desorption attached column (3), described thermal desorption attached column (3) effluent liquid, concentrated base flow container (24), the electrode probe (17) of pH meter, pretreated anaerobic digestion liquid storage tank (18) and MgCl
2solution reservoir (21) all reclaims retort (15) and is connected with nutritive element.
Magnesium ammonium phosphate, also known as MAP, is commonly called as struvite, and chemical formula is MgNH
4pO
46H
2o is a kind of slow-release fertilizer of excellent property.
As time goes on magnesium ammonium phosphate can lose crystal water, part even all NH after temperature rises to certain limit
4 +-N, is decomposed into MgHPO
4, Mg
3(PO
4)
2, Mg
2p
2o
7mixture.And MgHPO
4with Mg
3(PO
4)
2to NH
4 +-N has adsorption function, wherein MgHPO
4to NH
4 +the adsorption effect of-N is very remarkable.By pyrolysis MAP, obtain pyrolysis product, suitable raw material can be provided for the nutritive element reclaimed in anaerobic digestion solution.
Municipal sludge is after Normal Temperature Anaerobic Digestion, get anaerobic digestion solution to leave standstill, employing aperture is the anaerobic digestion solution after the blend fiber membrane filtration of 0.45 μm is transparent yellowish, containing abundant solvability orthophosphoric acid salt, ammonia nitrogen simultaneously containing higher concentration, and containing a small amount of calcium ion, magnesium ion, sodium ion and chlorion etc.Anaerobic digestion solution COD concentration 140.8 ~ 372.7mg/L after filter, total organic carbon TOC concentration is 16.4 ~ 37.7mg/L, and solvability orthophosphoric acid salt concentration is 38.4 ~ 132.1mg/L, and ammonia nitrogen concentration is 117.0 ~ 465.3mg/L, Ca
2+concentration is 20.3 ~ 65.3mg/L, K
+concentration is 34.2 ~ 79.8mg/L, Mg
2+concentration is 57.8 ~ 65.8mg/L.
Anaerobic digestion solution after acidizing pretreatment is flowed through MAP pyrolysis product, and employing concentration is the sodium hydroxide solution control absorption reaction pH of 0.2mol/L is 8.0 ~ 10.0, obtains ammonia nitrogen absorption after product and also collects effluent liquid.Principal reaction can be represented by the formula:
Mg
2++HPO
4 2-+NH
4 ++6H
2O?MgNH
4PO
4·6H
2O↓+H
+
Along with the carrying out of MAP formation reaction, constantly there is H
+release, causes solution ph to decline, the carrying out of inhibited reaction.In addition, excessive Mg
2+also likely with OH
-complexing, generation complex compound [Mg(OH)]
+, equally also can release H
+, pH is reduced further.Therefore, must add in alkali and the H produced
+, reaction just can be made to carry out to the direction being conducive to generating MAP.Keep absorption reaction pH can form more magnesium ammonium phosphate sediment, keep absorption reaction pH can improve the ammonia nitrogen rate of recovery of anaerobic digestion solution.
Solvability orthophosphoric acid salt in effluent liquid after ammonia nitrogen reclaims and Mg
2+concentration is respectively 110.5 ~ 226.9mg/L and 85.5 ~ 170.3mg/L.Add the effluent liquid after ammonia nitrogen recovery in pretreated anaerobic digestion solution according to reaction phosphorus nitrogen mol ratio 0.8 ~ 1.2: 1, form mixed solution, add part MgCl according to reaction magnesium nitrogen mol ratio 1.5 ~ 2.0: 1 simultaneously
2solution, employing concentration is that the sodium hydroxide solution of 4.0mol/L controls reaction pH 7.0 ~ 10.0, obtains throw out, dries throw out acquisition fresh feed; In mixed solution, the rate of recovery of nitrogen and phosphorus can reach more than 91% and 92% respectively.The principal reaction obtaining this fresh feed can be represented by the formula:
Mg
2++PO
4 3-+NH
4 ++6H
2O?MgNH
4PO
4·6H
2O↓
React phosphorus nitrogen mol ratio, reaction magnesium nitrogen mol ratio and reaction pH in nutritive element removal process and have material impact to nitrogen phosphorous recovery.Reaction phosphorus nitrogen mol ratio, reaction magnesium nitrogen mol ratio determine nitrogen phosphorus magnesium ion starting point concentration in reaction forward slip value liquid; Reaction pH determines the existence form of phosphate radical in mixed solution.
The analysis means such as fourier infrared (FTIR), X-ray diffraction (XRD), inductively coupled plasma direct reading spectrometry (ICP) and scanning electronic microscope (SEM) and power spectrum (EDS) are utilized to carry out analysis and characterization to fresh feed character.Fresh feed is hardly containing organic; Except containing Ca, Mg, the metallic elements such as Na, Al, Fe also containing minute quantity, heavy metal content is extremely low; Fresh feed, can carry out pyrolysis, absorption, recycle again.
Beneficial effect: compared with the method for existing recovery urban mud anaerobic digestion solution Middle nutrition element, the outstanding advantages that the present invention has comprises: the method 1) adopting dry type pyrolysis under cryogenic, both the separation having achieved nitrogen in anaerobic digestion solution concentrates, and additionally reduces energy consumption of reaction; 2) adopt the device of integrated pyrolysis and absorption when running, regulate and control convenient, easy handling maintenance; 3) efficiency that simultaneously reclaims of nitrogen phosphorus is higher, can reach more than 91% and 92% respectively; 4) removal process is without the need to supplementary phosphorus source, and nutritive element reclaims after product and can reuse in nitrogen phosphorus removal process; 5) in final thermal desorption attached column, material can be used as a kind of rich Rock Phosphate (72Min BPL) discharge of excellent property.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the special purpose device of the method reclaiming nitrogen phosphorus in urban mud anaerobic digestion solution.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated.
As shown in Figure 1, for the special purpose device of the method for nitrogen phosphorus in recovery urban mud anaerobic digestion solution of the present invention, comprise thermostatic water-circulator bath pot 1, thermal plume of air 2, thermal desorption attached column 3, air pump 4, glass rotameter 5, siccative 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, diluted alkaline flow container 11, sig water supply pump 12, sig water control valve 13, magnetic stirring apparatus 14, nutritive element reclaims 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, pretreated anaerobic digestion hydraulic control valve 20, MgCl
2solution reservoir 21, MgCl
2solution supply pump 22, MgCl
2solution control valve 23, concentrated base flow container 24, high alkali liquid supply pump 25, high alkali liquid control valve 26, pyrolysis absorption raw material 27, thermal desorption attached column filter core 28, thermal plume of air filtration core 29, feed box 30.This device controls the temperature of heating by thermostatic water-circulator bath pot 1, thermal plume of air 2 is connected at circulating water intake place, circulating water outlet place connects the thermal desorption attached column 3 that pyrolysis absorption raw material is housed, air pump 4 supply air through glass rotameter 5 be metered into thermal plume of air 2 warm air, via thermal desorption attached column 3 by pyrogenous origin for MAP NH
3bring the absorption bottle 7 connecting and dilute sulphuric acid is housed into, siccative 6 is for avoiding the impact of pyrogenous origin water vapor.Closedown thermostatic water-circulator bath pot 1 after pyrolysis completes, after thermal desorption attached column 3 is cooled to room temperature, upper prop anaerobic digestion solution squeezes into thermal desorption attached column 3 by upper prop anaerobic digestion fluid supply pump 9, sodium hydroxide sig water is squeezed into by sig water supply pump 12 simultaneously, obtain pyrolysis absorption raw material 27, effluent liquid flows into nutritive element and reclaims retort 15, and pretreated anaerobic digestion solution is by pretreated anaerobic digestion fluid supply pump 19, MgCl simultaneously
2solution is by MgCl
2solution supply pump 22, sodium hydroxide high alkali liquid are squeezed into nutritive element by high alkali liquid supply pump 25 and are reclaimed retort 15, regulate the rotating speed of magnetic stirring apparatus 14, reaction pH is controlled by pH meter 16, mixed system after having reacted pours feed box 30 into, throw out after solid-liquid separation obtains the pyrolysis absorption raw material of fresh feed as recycling after drying, transfer in thermal desorption attached column 3, adsorb raw material 27 mix with pyrolysis, again carry out pyrolysis, absorption, cyclical operation.
Solvability orthophosphoric acid salt (SOP, in P) concentration, the ammonia nitrogen (NH of effluent liquid in following embodiment is measured respectively with molybdenum-antimony anti-spectrophotometric method, Berthelot spectrophotometry, ion chromatography and potassium dichromate process
4 +-N) concentration, magnesium ion concentration and COD concentration.
Pyrolysis in following embodiment is adsorbed phosphorous rate, the Nitrogen content of raw material and is described as follows containing magnesium rate computation process:
Accurately take 40 ~ 45 DEG C of pyrolysis absorption raw material M gram of drying, be dissolved in V milliliter dilute hydrochloric acid completely, solvability orthophosphoric acid salt (SOP, in the P) concentration using molybdenum-antimony anti-spectrophotometric method, Berthelot spectrophotometry and this solution of ion-chromatographic determination is respectively C
1mg/L, ammonia nitrogen concentration are C
2mg/L and magnesium ion concentration C
3mg/L.Then, the M gram of phosphorous quality of product is (C
1× V ÷ 1000) milligram, nitrogenous quality is (C
2× V ÷ 1000) milligram is (C containing magnesia amount
3× V ÷ 1000) milligram.
The phosphorous rate of pyrolysis absorption raw material is with P
2o
5meter=[(C
1× V ÷ 1000) × (142 ÷ 62)] ÷ (M × 1000) × 100%;
Pyrolysis absorption raw material Nitrogen content is with NH
4 +-N meter=(C
2× V ÷ 1000) ÷ (M × 1000) × 100%;
Pyrolysis absorption raw material contains magnesium rate in MgO=[(C
3× V ÷ 1000) × (40 ÷ 24)] ÷ (M × 1000) × 100%.
Embodiment 1
MAP dry at 40 ~ 45 DEG C to constant weight sealing save backup.
Get MAP and be about 6.2g(1BV=10mL) be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 2h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ammonia nitrogen amount removed is 66.8mg.
Municipal sludge is after Normal Temperature Anaerobic Digestion, employing aperture is the blend fiber membrane filtration of 0.45 μm, obtain the rear anaerobic digestion solution of filter, the rear anaerobic digestion solution pH of filter is regulated to be 3.5 ~ 4.0 with the hydrochloric acid of 2.0mol/L, obtain pretreated anaerobic digestion solution, recording initial COD concentration is 194.1mg/L, initial NH
4 +-N, SOP and magnesium ion concentration are respectively 173.7mg/L, 46.8mg/L and 32.5mg/L.
Pretreated anaerobic digestion solution pH is regulated to be 10.0 with the sodium hydroxide solution of 4.0mol/L, obtain upper prop anaerobic digestion solution, carry out falling streaming with the flow velocity of 2BV/h and run ammonia nitrogen in absorption upper prop anaerobic digestion solution, the sodium hydroxide solution of 0.2mol/L is constantly supplemented by sig water supply pump, it is 10.0 that run duration controls absorption reaction pH, collect effluent liquid, adsorb rear acquisition ammonia nitrogen absorption after product.The COD mean concns recording effluent liquid is 172.1mg/L; NH
4 +the mean concns of-N is 1.1mg/L; The mean concns of SOP is 202.1mg/L; The mean concns of magnesium ion is 239.9mg/L; Upper prop anaerobic digestion solution treatment capacity reaches 28BV.
At 40 ~ 45 DEG C, dry ammonia nitrogen absorption after product, measure by analysis, the phosphorous rate of ammonia nitrogen absorption after product is 31.9%, Nitrogen content is 4.3%, be 19.3% containing magnesium rate, in ammonia nitrogen absorption after product magnesium hydroxide and magnesium pyrophosphate composition 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 liquid, obtains mixed solution; Part MgCl is added by reaction magnesium nitrogen mol ratio 1.8: 1
2solution is in mixed solution; Controlling reaction pH with 4.0mol/L sodium hydroxide solution is 9.0, under 200rpm rotating speed, react 30min, obtains throw out and supernatant liquor; The NH of supernatant liquor
4 +-N concentration is the concentration of 12.8mg/L, SOP is 10.1mg/L.
Throw out is dried at 40 ~ 45 DEG C, obtains fresh feed.Measure by analysis, the phosphorous rate of fresh feed is 26.4%, and Nitrogen content is 4.6%, is 18.2% containing magnesium rate, and fresh feed magnesium hydroxide is little, hardly containing organic and heavy metal.
Fresh feed is transferred in thermal desorption attached column, for the pyrolysis of next time.
Embodiment 2
Get appropriate MAP and be placed in thermal desorption attached column, control pyrolysis temperature 80 DEG C, pyrolysis time 2h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ratio that the ammonia-nitrogen content that acquisition steams accounts for MAP nitrogen content is the pyrolysis product of 17.7%.
Embodiment 3
Get appropriate MAP and be placed in thermal desorption attached column, control pyrolysis temperature 90 DEG C, pyrolysis time 2h, air flow/quality is 4.8m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ratio that the ammonia-nitrogen content that acquisition steams accounts for MAP nitrogen content is the pyrolysis product of 23.1%.
Embodiment 4
Get appropriate MAP and be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 2h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 2.17kgm
-2, the ratio that the ammonia-nitrogen content that acquisition steams accounts for MAP nitrogen content is the pyrolysis product of 12.5%.
Embodiment 5
Get appropriate MAP and be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 1h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ratio that the ammonia-nitrogen content that acquisition steams accounts for MAP nitrogen content is the pyrolysis product of 2.3%.
Embodiment 6
Get appropriate MAP and be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 3h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ratio that the ammonia-nitrogen content that acquisition steams accounts for MAP nitrogen content is the pyrolysis product of 31.0%.
Embodiment 7
Get appropriate MAP and be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 2h, air flow/quality is 9.6m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ratio that the ammonia-nitrogen content that acquisition steams accounts for MAP nitrogen content is the pyrolysis product of 28.1%.
Embodiment 8
Get appropriate MAP and be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 2h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 1.56kgm
-2, the ratio that the ammonia-nitrogen content that acquisition steams accounts for MAP nitrogen content is the pyrolysis product of 18.3%.
Embodiment 9
Get appropriate MAP and be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 2h, air flow/quality is 1.2m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ratio that the ammonia-nitrogen content that acquisition steams accounts for MAP nitrogen content is the pyrolysis product of 3.2%.
Embodiment 10
In Example 1, MAP is about 6.2g(1BV=10mL) be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 2h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ammonia nitrogen amount removed is 66.4mg.
Pretreated anaerobic digestion solution in Example 1, pretreated anaerobic digestion solution pH is regulated to be 8.0 with the sodium hydroxide solution of 4.0mol/L, obtain upper prop anaerobic digestion solution, carry out falling streaming with the flow velocity of 2BV/h and run ammonia nitrogen in absorption upper prop anaerobic digestion solution, constantly supplemented the sodium hydroxide solution of 0.2mol/L by sig water supply pump, collect effluent liquid.The COD mean concns recording effluent liquid is 154.6mg/L; NH
4 +the mean concns of-N is 5.5mg/L; The mean concns of SOP is 378.6mg/L; The mean concns of magnesium ion is 520.5mg/L.
Embodiment 11
In Example 1, MAP is about 6.2g(1BV=10mL) be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 2h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ammonia nitrogen amount removed is 67.0mg.
Pretreated anaerobic digestion solution in Example 1, pretreated anaerobic digestion solution pH is regulated to be 9.0 with the sodium hydroxide solution of 4.0mol/L, obtain upper prop anaerobic digestion solution, carry out falling streaming with the flow velocity of 2BV/h and run ammonia nitrogen in absorption upper prop anaerobic digestion solution, constantly supplemented the sodium hydroxide solution of 0.2mol/L by sig water supply pump, collect effluent liquid.The COD mean concns recording effluent liquid is 174.1mg/L; NH
4 +the mean concns of-N is 6.4mg/L; The mean concns of SOP is 205.1mg/L; The mean concns of magnesium ion is 293.7mg/L.
Embodiment 12
In Example 1, MAP is about 6.2g(1BV=10mL) be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 2h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ammonia nitrogen amount removed is 71.0mg.
Pretreated anaerobic digestion solution in Example 1, pretreated anaerobic digestion solution pH is regulated to be 9.5 with the sodium hydroxide solution of 4.0mol/L, obtain upper prop anaerobic digestion solution, carry out falling streaming with the flow velocity of 5BV/h and run ammonia nitrogen in absorption upper prop anaerobic digestion solution, constantly supplemented the sodium hydroxide solution of 0.2mol/L by sig water supply pump, collect effluent liquid.The COD mean concns recording effluent liquid is 145.5mg/L; NH
4 +the mean concns of-N is 7.9mg/L; The mean concns of SOP is 95.7mg/L; The mean concns of magnesium ion is 127.0mg/L.
Embodiment 13
In Example 1, MAP is about 6.2g(1BV=10mL) be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 2h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ammonia nitrogen amount removed is 66.8mg.
Pretreated anaerobic digestion solution in Example 1, pretreated anaerobic digestion solution pH is regulated to be 10.0 with the sodium hydroxide solution of 4.0mol/L, obtain upper prop anaerobic digestion solution, carry out falling streaming with the flow velocity of 2BV/h and run ammonia nitrogen in absorption upper prop anaerobic digestion solution, constantly supplemented the sodium hydroxide solution of 0.2mol/L by sig water supply pump, collect effluent liquid.The COD mean concns recording effluent liquid is 154.4mg/L; NH
4 +the mean concns of-N is 1.0mg/L; The mean concns of SOP is 202.1mg/L; The mean concns of magnesium ion is 239.9mg/L.
Embodiment 14
In Example 1, MAP is about 6.2g(1BV=10mL) be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 2h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ammonia nitrogen amount removed is 66.8mg.
Pretreated anaerobic digestion solution in Example 1, pretreated anaerobic digestion solution pH is regulated to be 9.5 with the sodium hydroxide solution of 4.0mol/L, obtain upper prop anaerobic digestion solution, carry out falling streaming with the flow velocity of 1BV/h and run ammonia nitrogen in absorption upper prop anaerobic digestion solution, constantly supplemented the sodium hydroxide solution of 0.2mol/L by sig water supply pump, collect effluent liquid.The COD mean concns recording effluent liquid is 160.2mg/L; NH
4 +the mean concns of-N is 0.6mg/L; The mean concns of SOP is 124.3mg/L; The mean concns of magnesium ion is 192.5mg/L.
Embodiment 15
Measure the effluent liquid character after ammonia nitrogen absorption: NH
4 +-N concentration is the concentration of 12.8mg/L, SOP is 227.0mg/L, and 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 liquid, obtains mixed solution; Part MgCl is added by reaction magnesium nitrogen mol ratio 2.0: 1
2solution is in mixed solution; Controlling reaction pH with 4.0mol/L sodium hydroxide solution is 8.0, under 200rpm rotating speed, react 30min, obtains throw out and supernatant liquor; The NH of supernatant liquor
4 +-N concentration is 34.7mg/L, NH in mixed solution
4 +the rate of recovery of-N is 50.2%; The concentration of SOP is 93.7mg/L, and in mixed solution, the rate of recovery of SOP is 40.2%.
Throw out after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Measure by analysis, the phosphorous rate 26.4% of fresh feed, Nitrogen content is 4.6%, is 21.9% containing magnesium rate, and in fresh feed, magnesium hydroxide is little, hardly containing organic and heavy metal.
Embodiment 16
Mixed solution in Example 15, is added in obtained effluent liquid by reaction phosphorus nitrogen mol ratio 1.0: 1 by pretreated anaerobic digestion solution, obtains mixed solution; Part MgCl is added by reaction magnesium nitrogen mol ratio 2.0: 1
2solution is in mixed solution; Controlling reaction pH with 4.0mol/L sodium hydroxide solution is 10.0, under 200rpm rotating speed, react 30min, obtains throw out and supernatant liquor; The NH of supernatant liquor
4 +-N concentration is 29.3mg/L, NH in mixed solution
4 +the rate of recovery of-N is 82.2%; The concentration of SOP is 0mg/L, and in mixed solution, the rate of recovery of SOP is 100%.
Throw out after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Measure by analysis, the phosphorous rate of fresh feed is 37.9%, and Nitrogen content is 4.2%, is 18.4% containing magnesium rate, and in fresh feed, magnesium hydroxide is little, hardly containing organic and heavy metal.
Embodiment 17
Mixed solution in Example 15, is added in obtained effluent liquid by reaction phosphorus nitrogen mol ratio 1.2: 1 by pretreated anaerobic digestion solution, obtains mixed solution; Part MgCl is added by reaction magnesium nitrogen mol ratio 2.0: 1
2solution is in mixed solution; Controlling reaction pH with 4.0mol/L sodium hydroxide solution is 9.0, under 200rpm rotating speed, react 30min, obtains throw out and supernatant liquor; The NH of supernatant liquor
4 +-N concentration is 27.4mg/L, NH in mixed solution
4 +the rate of recovery of-N is 55.7%; The concentration of SOP is 80.5mg/L, and in mixed solution, the rate of recovery of SOP is 51.1%.
Throw out after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Measure by analysis, the phosphorous rate of fresh feed is 27.9%, and Nitrogen content is 4.9%, is 18.2% containing magnesium rate, and in fresh feed, magnesium hydroxide is little, hardly containing organic and heavy metal.
Embodiment 18
Mixed solution in Example 15, is added in obtained effluent liquid by reaction phosphorus nitrogen mol ratio 0.8: 1 by pretreated anaerobic digestion solution, obtains mixed solution; Part MgCl is added by reaction magnesium nitrogen mol ratio 2.0: 1
2solution is in mixed solution; Controlling reaction pH with 4.0mol/L sodium hydroxide solution is 9.0, under 200rpm rotating speed, react 30min, obtains throw out and supernatant liquor; The NH of supernatant liquor
4 +-N concentration is 21.9mg/L, NH in mixed solution
4 +the rate of recovery of-N is 72.5%; The concentration of SOP is 6.0mg/L, and in mixed solution, the rate of recovery of SOP is 95.9%.
Throw out after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Measure by analysis, the phosphorous rate of fresh feed is 23.5%, and Nitrogen content is 4.9%, is 18.6% containing magnesium rate, and in fresh feed, magnesium hydroxide is little, hardly containing organic and heavy metal.
Embodiment 19
Mixed solution in Example 15, is added in obtained effluent liquid by reaction phosphorus nitrogen mol ratio 1.0: 1 by pretreated anaerobic digestion solution, obtains mixed solution; Part MgCl is added by reaction magnesium nitrogen mol ratio 1.5: 1
2solution is in mixed solution; Controlling reaction pH with 4.0mol/L sodium hydroxide solution is 9.0, under 200rpm rotating speed, react 30min, obtains throw out and supernatant liquor; The NH of supernatant liquor
4 +-N concentration is 25.6mg/L, NH in mixed solution
4 +the rate of recovery of-N is 63.3%; The concentration of SOP is 6.0mg/L, and in mixed solution, the rate of recovery of SOP is 96.2%.
Throw out after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Measure by analysis, the phosphorous rate of fresh feed is 28.6%, and Nitrogen content is 5.8%, is 17.4% containing magnesium rate, and in fresh feed, magnesium hydroxide is little, hardly containing organic and heavy metal.
Embodiment 20
Mixed solution in Example 15, is added in obtained effluent liquid by reaction phosphorus nitrogen mol ratio 1.0: 1 by pretreated anaerobic digestion solution, obtains mixed solution; Part MgCl is added by reaction magnesium nitrogen mol ratio 1.8: 1
2solution is in mixed solution; Controlling reaction pH with 4.0mol/L sodium hydroxide solution is 9.0, under 200rpm rotating speed, react 30min, obtains throw out and supernatant liquor; The NH of supernatant liquor
4 +-N concentration is 0mg/L, NH in mixed solution
4 +the rate of recovery of-N is 100%; The concentration of SOP is 12.0mg/L, and in mixed solution, the rate of recovery of SOP is 92.3%.
Throw out after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Measure by analysis, the phosphorous rate of fresh feed is 26.8%, and Nitrogen content is 6.2%, is 17.4% containing magnesium rate, and in fresh feed, magnesium hydroxide is little, hardly containing organic and heavy metal.
Embodiment 21
Mixed sediment in Example 1 carries out pyrolysis again, and control pyrolysis temperature 100 DEG C, pyrolysis time 2h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ammonia nitrogen amount removed is 49.5mg, and ammonia nitrogen enriching quantity is 115.6mg.
Pretreated anaerobic digestion solution in Example 1, be 10.0 with the pretreated anaerobic digestion solution pH of the sodium hydroxide solution of 4.0mol/L, carry out falling streaming with the flow velocity of 2BV/h and run ammonia nitrogen in absorption upper prop anaerobic digestion solution, the sodium hydroxide solution of 0.2mol/L is constantly supplemented by sig water supply pump, it is 10.0 that run duration controls absorption reaction pH, collect effluent liquid, adsorb rear acquisition ammonia nitrogen absorption after product.The COD mean concns recording effluent liquid is 183.2mg/L; NH
4 +the mean concns of-N is 2.4mg/L; The mean concns of SOP is 232.1mg/L; The mean concns of magnesium ion is 120.0mg/L; Upper prop anaerobic digestion solution treatment capacity reaches 240mL.
The phosphorous rate of ammonia nitrogen absorption postprecipitation thing is 38.7%, and Nitrogen content is 6.2%, is 26.0% containing magnesium rate, hardly containing organic and heavy metal, is a kind of rich Rock Phosphate (72Min BPL) of excellent property.
By reaction phosphorus nitrogen mol ratio 1.0: 1, pretreated anaerobic digestion solution is added in obtained effluent liquid, obtains mixed solution; Part MgCl is added by reaction magnesium nitrogen mol ratio 1.8: 1
2solution is in mixed solution; Controlling reaction pH with 4.0mol/L sodium hydroxide solution is 9.0, reacts 30min, suction filtration under 200rpm rotating speed, obtains throw out and supernatant liquor; The NH of supernatant liquor
4 +-N concentration is the concentration of 12.5mg/L, SOP is 9.3mg/L.
Throw out after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Measure by analysis, the phosphorous rate of fresh feed is 26.8%, and Nitrogen content is 6.2%, is 17.5% containing magnesium rate, and in fresh feed, magnesium hydroxide composition increases, hardly containing organic and heavy metal.
Fresh feed is transferred in thermal desorption attached column, for the pyrolysis of next time.
Embodiment 22
Get MAP and be about 6.2g(1BV=10mL) be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 2h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ammonia nitrogen amount removed is 80.1mg.
Pretreated anaerobic digestion solution in Example 1, pretreated anaerobic digestion solution pH is regulated to be 10.0 with the sodium hydroxide solution of 4.0mol/L, carry out falling streaming with the flow velocity of 2BV/h and run ammonia nitrogen in absorption upper prop anaerobic digestion solution, the sodium hydroxide solution of 0.2mol/L is constantly supplemented by sig water supply pump, it is 10.0 that run duration controls absorption reaction pH, collect effluent liquid, adsorb rear acquisition ammonia nitrogen absorption after product.The COD mean concns recording effluent liquid is 163.5mg/L; NH
4 +the mean concns of-N is 1.6mg/L; The mean concns of SOP is 163.5mg/L; The mean concns of magnesium ion is 134.1mg/L; Upper prop anaerobic digestion solution treatment capacity reaches 280mL.
At 40 ~ 45 DEG C, dry ammonia nitrogen absorption after product, measure by analysis, the phosphorous rate of ammonia nitrogen absorption after product is 26.3%, Nitrogen content is 5.2%, be 15.4% containing magnesium rate, in ammonia nitrogen absorption after product magnesium hydroxide and magnesium pyrophosphate composition less, hardly containing organic and heavy metal.
After having adsorbed, according to the pyrolysis again of pyrolytical condition before, obtaining ammonia nitrogen removal amount is 44.8mg, and ammonia nitrogen enriching quantity is 124.9mg.
Pretreated anaerobic digestion solution in Example 1, adsorbs again according to adsorption conditions before, collects effluent liquid.The COD mean concns recording effluent liquid is 154.6mg/L; NH
4 +the mean concns of-N is 3.4mg/L; The mean concns of SOP is 75.1mg/L; The mean concns of magnesium ion is 174.0mg/L; Upper prop anaerobic digestion solution treatment capacity reaches 240mL.
Measure by analysis, the phosphorous rate of ammonia nitrogen absorption after product is 24.2%, and Nitrogen content is 5.2%, be 35.5% containing magnesium rate, in ammonia nitrogen absorption after product, magnesium hydroxide and magnesium pyrophosphate composition increase to some extent, hardly containing organic and heavy metal, are a kind of rich Rock Phosphate (72Min BPL) of excellent property.
The effluent liquid of twice is mixed, by reaction phosphorus nitrogen mol ratio 1.0: 1, pretreated anaerobic digestion solution is added in obtained effluent liquid; Part MgCl is added by reaction magnesium nitrogen mol ratio 1.8: 1
2solution is in mixed solution; Controlling reaction pH with 4.0mol/L sodium hydroxide solution is 9.0, under 200rpm rotating speed, react 30min, obtains throw out and supernatant liquor; The NH of supernatant liquor
4 +-N concentration is the concentration of 17.4mg/L, SOP is 11.6mg/L.
Throw out after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed.Measure by analysis, the phosphorous rate of fresh feed is 20.3%, and Nitrogen content is 8.7%, is 17.5% containing magnesium rate, hardly containing organic and heavy metal in fresh feed.
Embodiment 23
Starting: get MAP and be about 6.2g(1BV=10mL) be placed in thermal desorption attached column, control pyrolysis temperature 100 DEG C, pyrolysis time 2h, air flow/quality is 2.4m
3h
-1kg
-1, quality/contact area is 0.78kgm
-2, the ammonia nitrogen amount steamed is 66.1mg.
Pretreated anaerobic digestion solution in Example 1, pretreated anaerobic digestion solution pH is regulated to be 10.0 with the sodium hydroxide solution of 4.0mol/L, obtain upper prop anaerobic digestion solution, carry out falling streaming with the flow velocity of 2BV/h and run ammonia nitrogen in absorption upper prop anaerobic digestion solution, the sodium hydroxide solution of 0.2mol/L is constantly supplemented by sig water supply pump, it is 10.0 that run duration controls absorption reaction pH, collects effluent liquid.
Think that ammonia nitrogen absorption completes when ammonia nitrogen mean concns is greater than 0 in effluent liquid.Detect effluent liquid NH
4 +the mean concns of-N is 1.1mg/L; The mean concns of SOP is 202.1mg/L; The mean concns of magnesium ion is 239.9mg/L; In ammonia nitrogen absorption process, anaerobic digestion solution treatment capacity reaches 280mL.
Ammonia nitrogen absorption completes after product and dries at 40 ~ 45 DEG C, and obtain absorption after product 5374.3mg, its phosphorous rate is 28.6%, and Nitrogen content is 8.5%, is 15.6% containing magnesium rate.
By reaction phosphorus nitrogen mol ratio 1.0: 1, pretreated anaerobic digestion solution 155mL is added in obtained effluent liquid, obtains mixed solution; Part MgCl is added by reaction magnesium nitrogen mol ratio 1.8: 1
2solution is in mixed solution; Controlling reaction pH with 4.0mol/L sodium hydroxide solution is 9.0, and under 200rpm rotating speed, react 30min, the throw out after filtration is dried at 40 ~ 45 DEG C, obtains fresh feed 402.5mg.
Circulation 1: transferred to by fresh feed in thermal desorption attached column, the ammonia nitrogen amount that pyrolysis steams is 49.5mg, carries out adsorption operations, detects effluent liquid NH
4 +the mean concns of-N is 2.4mg/L; The mean concns of SOP is 67.6mg/L; The mean concns of magnesium ion is 120.0mg/L; In ammonia nitrogen absorption process, upper prop anaerobic digestion solution treatment capacity reaches 240mL.Obtain ammonia nitrogen absorption after product 5232.6mg, its phosphorous rate is 40.9%, and Nitrogen content is 8.4%, is 35.3% containing magnesium rate.In nutritive element removal process, pretreated anaerobic digestion solution treatment capacity is 52mL, and obtain fresh feed 134.6mg, its phosphorous rate is 32.9%, and Nitrogen content is 4.6%, is 24.3% containing magnesium rate.
Circulation 2: transferred to by fresh feed in thermal desorption attached column, the ammonia nitrogen amount that pyrolysis steams is 36.7mg, carries out adsorption operations, detects effluent liquid NH
4 +the mean concns of-N is 6.2mg/L; The mean concns of SOP is 144.8mg/L; The mean concns of magnesium ion is 76.9mg/L; In ammonia nitrogen absorption process, upper prop anaerobic digestion solution treatment capacity reaches 160mL.Obtain ammonia nitrogen absorption after product 5195.8mg, its phosphorous rate is 38.7%, and Nitrogen content is 6.2%, is 31.7% containing magnesium rate.In nutritive element removal process, pretreated anaerobic digestion solution treatment capacity is 79mL, and obtain fresh feed 206.0mg, its phosphorous rate is 34.8%, and Nitrogen content is 4.6%, is 25.0% containing magnesium rate.
Circulation 3: transferred to by fresh feed in thermal desorption attached column, the ammonia nitrogen amount that pyrolysis steams is 29.1mg, carries out adsorption operations, detects effluent liquid NH
4 +the mean concns of-N is 9.1mg/L; The mean concns of SOP is 77.3mg/L; The mean concns of magnesium ion is 36.9mg/L; In ammonia nitrogen absorption process, upper prop anaerobic digestion solution treatment capacity reaches 160mL.Obtain ammonia nitrogen absorption after product 5009.7mg, its phosphorous rate is 36.3%, and Nitrogen content is 5.5%, is 27.6% containing magnesium rate.In nutritive element removal process, pretreated anaerobic digestion solution treatment capacity is 42mL, and obtain fresh feed 110.0mg, its phosphorous rate is 31.2%, and Nitrogen content is 5.3%, is 29.1% containing magnesium rate.
Circulation 4: transferred to by fresh feed in thermal desorption attached column, the ammonia nitrogen amount that pyrolysis steams is 22.8mg, carries out adsorption operations, detects effluent liquid NH
4 +the mean concns of-N is 9.1mg/L; The mean concns of SOP is 66.0mg/L; The mean concns of magnesium ion is 72.5mg/L; In ammonia nitrogen absorption process, upper prop anaerobic digestion solution treatment capacity reaches 160mL.Obtain ammonia nitrogen absorption after product 4901.6mg, its phosphorous rate is 38.6%, and Nitrogen content is 5.6%, is 31.0% containing magnesium rate.In nutritive element removal process, pretreated anaerobic digestion solution treatment capacity is 37mL, and obtain fresh feed 94.8mg, its phosphorous rate is 32.4%, and Nitrogen content is 6.5%, be 43.5% containing magnesium rate.
Circulation 5: transferred to by fresh feed in thermal desorption attached column, the ammonia nitrogen amount that pyrolysis steams is 19.5mg, carries out adsorption operations, detects effluent liquid NH
4 +the mean concns of-N is 10.2mg/L; The mean concns of SOP is 48.8mg/L; The mean concns of magnesium ion is 64.3mg/L; In ammonia nitrogen absorption process, upper prop anaerobic digestion solution treatment capacity reaches 120mL.Obtain ammonia nitrogen absorption after product 4848.9mg, its phosphorous rate is 37.2%, and Nitrogen content is 9.3%, is 31.4% containing magnesium rate.In nutritive element removal process, pretreated anaerobic digestion solution treatment capacity is 27mL, and obtain fresh feed 69.4mg, its phosphorous rate is 34.4%, and Nitrogen content is 5.8%, is 31.5% containing magnesium rate.
Circulation 6: transferred to by fresh feed in thermal desorption attached column, the ammonia nitrogen amount that pyrolysis steams is 18.4mg, carries out adsorption operations, detects effluent liquid NH
4 +the mean concns of-N is 11.9mg/L; The mean concns of SOP is 31.5mg/L; The mean concns of magnesium ion is 39.8mg/L; In ammonia nitrogen absorption process, upper prop anaerobic digestion solution treatment capacity reaches 120mL.Obtain ammonia nitrogen absorption after product 4737.8mg, its phosphorous rate is 35.6%, and Nitrogen content is 10.0%, is 31.6% containing magnesium rate.In nutritive element removal process, pretreated anaerobic digestion solution treatment capacity is 14mL, and obtain fresh feed 35.9mg, its phosphorous rate is 34.9%, and Nitrogen content is 5.4%, is 34.7% containing magnesium rate.
Circulation 7: transferred to by fresh feed in thermal desorption attached column, the ammonia nitrogen amount that pyrolysis steams is 15.7mg.Illustrate that in thermal desorption attached column, mixture still has pyrolysis again, absorption ammonia nitrogen and reclaims the potentiality of nitrogen phosphorus.
Round-robin test is taken turns through 7, in thermal desorption attached column, material still has 4918.3mg, can be used as rich Rock Phosphate (72Min BPL) to discharge, and there is good ammonia nitrogen absorption performance, also can continue to use as ammonia nitrogen adsorbent, the TAN steamed is 257.8mg, and in ammonia nitrogen absorption process, upper prop anaerobic digestion solution process total amount reaches 1240mL, in nutritive element removal process, pretreated anaerobic digestion solution process total amount is 406mL, and co-processing anaerobic digestion solution total amount reaches 1646mL.
Above used fresh feed is the throw out raw material after drying prepared by a circulation.
Claims (10)
1. reclaim a method for nitrogen phosphorus in urban mud anaerobic digestion solution, it is characterized in that: in thermal desorption attached column, first pyrolysis is carried out to MAP and obtain absorption material, reclaim the ammonia that pyrolysis is discharged; Then pass into upper prop anaerobic digestion solution and carry out adsorption treatment, obtain effluent liquid; Detect the ammonia nitrogen concentration in effluent liquid, when ammonia nitrogen concentration is greater than 0, stop absorption, first supplement fresh feed, then carry out pyrolysis, reclaim the ammonia that pyrolysis is discharged, then continue absorption, detect and carry out cyclical operation; Wherein, fresh feed is add MgCl in the mixed solution of effluent liquid and pretreated anaerobic digestion solution
2the throw out that solution obtains raw material after drying; Reclaim ammonia and final thermal desorption attached column in material be nitrogen phosphorus reclaim product.
2. the method for nitrogen phosphorus in recovery urban mud anaerobic digestion solution according to claim 1, is characterized in that: comprise the following steps:
(1) urban mud anaerobic digestion solution is filtered, obtain the rear anaerobic digestion solution of filter, then with anaerobic digestion solution pH to 3.5 ~ 4.0 after hydrochloric acid adjustment filter, obtain pretreated anaerobic digestion solution; Regulate the pH of pretreated anaerobic digestion solution to be 8.0 ~ 10.0 with sodium hydroxide solution, obtain upper prop anaerobic digestion solution;
(2) controlling pyrolysis temperature is 80 ~ 100 DEG C, and pyrolysis time 1 ~ 3h, air flow/quality is 1.2 ~ 9.6m
3h
-1kg
-1, quality/contact area is 0.78 ~ 2.17kgm
-2, in thermal desorption attached column, carry out pyrolysis to MAP, the ammonia steamed is absorbed by the absorption bottle that dilute sulphuric acid is housed;
(3) upper prop anaerobic digestion solution is passed into thermal desorption attached column, carry out falling streaming with the flow velocity of 1 ~ 5BV/h and run, it is 8.0 ~ 10.0 that run duration sodium hydroxide solution controls absorption reaction pH, obtains ammonia nitrogen absorption after product and collects effluent liquid;
(4) be add effluent liquid in step (3) in pretreated anaerobic digestion solution in step (1), acquisition mixed solution at 0.8 ~ 1.2: 1 by reaction phosphorus nitrogen mol ratio; Be add MgCl at 1.5 ~ 2.0: 1 by reaction magnesium nitrogen mol ratio
2solution is in mixed solution; Controlling reaction pH with sodium hydroxide solution is 7.0 ~ 10.0, under 200rpm rotating speed, react 30min, obtains throw out and supernatant liquor;
(5) by step (3) continuous adsorption, detect the ammonia nitrogen concentration in effluent liquid, when ammonia nitrogen concentration is greater than 0, stop absorption;
(6) dry throw out, obtain fresh feed; First transfer fresh raw material in thermal desorption attached column, then carries out cyclical operation by step (2) ~ (5); Reclaim ammonia and final thermal desorption attached column in material be nitrogen phosphorus reclaim product.
3. the method for nitrogen phosphorus in recovery urban mud anaerobic digestion solution according to claim 2, is characterized in that: in step (1), adopts aperture to be that the blend fiber membrane filtration of 0.45 μm removes suspended substance and part in urban mud anaerobic digestion solution organic.
4. the method for nitrogen phosphorus in recovery urban mud anaerobic digestion solution according to claim 2, is characterized in that: in step (1), adopts concentration to be that the hydrochloric acid of 2.0mol/L regulates anaerobic digestion solution pH after filter to be 4.0; Employing concentration is that the sodium hydroxide solution of 4.0mol/L regulates the pH of pretreated anaerobic digestion solution to be 10.0.
5. the method for nitrogen phosphorus in recovery urban mud anaerobic digestion solution according to claim 2, is characterized in that: in step (3), adopts concentration to be that to control absorption reaction pH be 10.0 for the sodium hydroxide solution of 0.2mol/L; Ammonia nitrogen absorption after product Nitrogen content is with NH
4 +-N counts 4 ~ 10%, and phosphorous rate is with P
2o
5count 24 ~ 41%, count 15 ~ 36% containing magnesium rate with MgO.
6. the method for nitrogen phosphorus in recovery urban mud anaerobic digestion solution according to claim 2, is characterized in that: in step (4), adopts concentration to be that to control reaction pH be 9.0 for the sodium hydroxide solution of 4.0mol/L.
7. the method for nitrogen phosphorus in recovery urban mud anaerobic digestion solution according to claim 2, is characterized in that: in step (4), and 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.
8. the method for nitrogen phosphorus in recovery urban mud anaerobic digestion solution according to claim 2, is characterized in that: in step (4), in mixed solution, the rate of recovery of nitrogen and phosphorus can reach more than 91% and 92% respectively; Fresh feed Nitrogen content is with NH
4 +-N counts 4 ~ 9%, and phosphorous rate is with P
2o
5count 20 ~ 38%, count 17 ~ 44% containing magnesium rate with MgO.
9. the method for nitrogen phosphorus in recovery urban mud anaerobic digestion solution according to claim 2, it is characterized in that: in step (6), drying sedimentary temperature is 40 ~ 45 DEG C.
10. the special purpose device of the method for nitrogen phosphorus in recovery urban mud anaerobic digestion solution according to claim 1, is characterized in that: comprise thermostatic water-circulator bath pot (1), thermal plume of air (2), thermal desorption attached column (3), air pump (4), siccative (6), absorption bottle (7), upper prop anaerobic digestion liquid storage tank (8), pretreated anaerobic digestion liquid storage tank (18), diluted alkaline flow container (11), MgCl
2solution reservoir (21), concentrated base flow container (24), nutritive element reclaim retort (15), pH meter (16), the electrode probe (17) of pH meter, feed box (30), described thermostatic water-circulator bath pot (1) is connected with thermal plume of air (2), described thermal plume of air (2) is connected with thermal desorption attached column (3), described air pump (4), glass rotameter (5) is connected with thermal plume of air (2), siccative (6) is established in thermal desorption attached column (3), described absorption bottle (7) is connected with thermal desorption attached column (3), described upper prop anaerobic digestion liquid storage tank (8) is connected with thermal desorption attached column (3), described thermal desorption attached column (3) effluent liquid, concentrated base flow container (24), the electrode probe (17) of pH meter, pretreated anaerobic digestion liquid storage tank (18) and MgCl
2solution reservoir (21) all reclaims retort (15) and is connected with nutritive element.
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