CN104229999B - A kind of filler for artificial swamp water treatment and preparation method thereof - Google Patents
A kind of filler for artificial swamp water treatment and preparation method thereof Download PDFInfo
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- CN104229999B CN104229999B CN201410467337.3A CN201410467337A CN104229999B CN 104229999 B CN104229999 B CN 104229999B CN 201410467337 A CN201410467337 A CN 201410467337A CN 104229999 B CN104229999 B CN 104229999B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The present invention relates to a kind of filler for artificial swamp water treatment and preparation method thereof, object is to provide a kind of artificial swamp new packing and preparation method thereof that simultaneously can realize slow-release oxygen, intensified denitrification and dephosphorization.For a filler for artificial swamp water treatment, described filler is ease up oxygen-release material, particle diameter of supported rare earth nitrogen phosphorus adsorbent is the volcanic cinder particle of 5-15mm.The present invention can improve the sewage purification ability of artificial swamp, and the method has the features such as technique is simple, raw material is sufficient, with low cost.
Description
Technical field
The invention belongs to environmental technology field, be specifically related to a kind of can synchronous slow oxygen, intensified denitrification and dephosphorization artificial swamp new packing, be applicable to the process compared with high ammonia-nitrogen wastewater of the sanitary sewage of villages and small towns or tourist attraction, polluted surface water, source, face sewage, sewage treatment plant tail water and concentration.
Background technology
Current China water environment situation worsens increasingly, has occurred the problems such as the organic contamination of lake eutrophication, immediate offshore area red tide, river and reservoir, has threatened the diversion safety of resident and the health of the people.Artificial wet land sewage treating process has the features such as effects of purification quality is good, capital construction working cost is low, energy consumption is low, maintenance management is simple, capacity of resisting impact load is strong due to it, and habitat can be provided, improve the aesthetic values of ecoscape, so be all widely used in sanitary sewage, trade effluent, agricultural area source sewage, urban storm runoff and eutrophication water etc. for wildlife.But from existing engineering practice, artificial swamp remains at some problems, the first is for hypoxgia.In artificial wet land system water inlet take that oxygen quantity is lower, air reaeration and root system of plant oxygen release limited in one's ability, particularly horizontal drowned flow type wetland, cannot meet the needs of a large amount of contaminant degradation.Dissolved oxygen deficiency will make many biologies not carry out normal aerobic repiration, and restriction nitration reaction, affects absorption and the excess accumulation of phosphorus, because the nitrifying process of organic aerobic degradation and denitrogenation all needs sufficient oxygen in sewage, otherwise reaction cannot be carried out; It two is that denitrification ability is limited.In Europe, the wetland ammonia nitrogen removal frank of long-time running is only 35% or 50%.Drowned flow artificial wet land be difficult to ensure needed for nitration denitrification aerobic/environment that replaces of anoxic and denitrification needed for carbon source; Three to be tp removal rates extend with working time and the limitation that declines for it.The absorption of gravel matrix to the phosphorus saturated life-span of existing extensive employing is shorter, is generally 2-3.And, after the plant of long-play wetland is withered, the phosphorus of absorption is released into wetland again.Above limiting factor becomes the bottleneck problem of Artificial Wetland Techniques further genralrlization and application.
Summary of the invention
The object of the present invention is to provide a kind of artificial swamp new packing and preparation method thereof that simultaneously can realize slow-release oxygen, intensified denitrification and dephosphorization, to solve above-mentioned Artificial Wetland Techniques Problems existing, improve its sewage purification ability, the method has the features such as technique is simple, raw material is sufficient, with low cost.
The technical scheme realizing the object of the invention is: a kind of filler for artificial swamp water treatment, and described filler is ease up oxygen-release material, particle diameter of supported rare earth nitrogen phosphorus adsorbent is the volcanic cinder particle of 5-15mm.
As a further improvement on the present invention, described rare earth nitrogen phosphorus adsorbent is the sorbent material containing lanthanum ion, and described slow-release oxygen material is calcium peroxide.
As a further improvement on the present invention, the loaded article on described volcanic cinder particle also comprises stearic acid and Macrogol 4000 mixture, quartz sand and flyash, and quartz sand and flyash contribute to the sedimentation of filler.
As a further improvement on the present invention, on described volcanic cinder particle, the weight percent of loaded article is: rare earth nitrogen phosphorus adsorbent 40-45%, slow-release oxygen material 30-35%, stearic acid and Macrogol 4000 mixture 5%, quartz sand 10-15%, flyash 5-10%.
The technical scheme realizing another goal of the invention of the present invention is: a kind of preparation method of the filler for artificial swamp water treatment, comprises the following steps:
Step 1 volcanic cinder and activator mix even, constant-pressure and high-temperature roasting for some time, after being cooled to room temperature, after being ground, add water, regulate silica alumina ratio, under room temperature condition, be placed on magnetic stirring apparatus, temperature rises to 90 DEG C of heating 2 hours, be warmed up to 95 DEG C of heating 2 hours again, filtering, washing to pH value is 7, puts into 80 DEG C, baking oven and dries 4 hours, obtain nitrogen absorber;
Step 2 by lanthanum concentration be 0.5% solution ph be adjusted to 10 gradually, according to solid-liquid mass ratio 1:50g/ml, add nitrogen absorber prepared by step 1, flood more than 16 hours, filter after filter cake in 110 DEG C of oven dry, and roasting, grinding sieve obtain nitrogen phosphorus adsorbent; 120 order particle diameter volcanic cinder particles after screening are best nitrogen phosphorus adsorbent;
The roasting under constant-pressure and high-temperature condition of step 3 Wingdale, add water after cooling reaction, dries the water that decrystallizes, and drops in hydrogen peroxide and soak, obtain oxygen-release material;
A certain amount of stearic acid and Macrogol 4000 are dissolved in tetracol phenixin by step 4, heating in water bath makes it dissolve completely, the oxygen-release material of preparation in the nitrogen phosphorus adsorbent then prepared by step 2 and step 3, and quartz sand (increases density of material, be conducive to formed material sedimentation), flyash (shock absorption) adds in proportion, its nitrogen phosphorus adsorbent 40-45%, slow-release oxygen material 30-35%, stearic acid and Macrogol 4000 mixture 5%, quartz sand 10-15%, flyash 5-10%.Be transferred to molding device after abundant stirring, carry out forced air drying after being pressed into different shapes and reclaim tetracol phenixin, the final Performance of Constructed Wetlands Substrates obtaining synchronous slow oxygen, intensified denitrification and dephosphorization.
In described step 1, activator refers to NaOH, and alkali and scoriaceous mass ratio are 1.0-1.5; Maturing temperature 500-900 DEG C, the time is 1-2 hour; Silica alumina ratio is adjusted to 5-8.
In described step 2, maturing temperature is 450-500 DEG C, and the time is 1 hour.
In described step 3, maturing temperature is 800-1200 DEG C, and the time is 1 hour; Bake out temperature is 105 DEG C, and the time is 1 hour.
In described step 4, the ratio of stearic acid and polyoxyethylene glycol is 1:1, and the ratio of this mixture in tetracol phenixin is 0.5%-1.5%, and the ratio in final product is 5%; Bath temperature 40-50 DEG C.The weight percent added to the material component in carbon tetrachloride solution and each component is nitrogen phosphorus adsorbent 40-45%, slow-release oxygen material 30-35%, stearic acid and Macrogol 4000 mixture 5%, quartz sand 10-15%, flyash 5-10%.
Beneficial effect
The present invention by synchronous slow oxygen, intensified denitrification and dephosphorization new packing as the matrix of artificial swamp, improve the removal ability to dirty Organic substance in water, nitrogen and phosphorus, improve effluent quality, its concrete advantage comprises:
(1) sufficient oxygen amount is provided.Sewage met by filler can discharge oxygen for a long time lentamente, ensures the oxygen level of wetland inner sustain abundance, and supply microorganism carries out organic matter degradation and nitration reaction, promotes pollutant removal.
(2) greatly phosphorus adsorptive power is improved.Containing lanthanum element in new packing of the present invention, have very strong characterization of adsorption to the positive phosphorus of negatively charged ion, lanthanum can generate lanthanum orthophosphate with orthophosphoric acid salt and precipitates simultaneously, is locked by phosphorus in its internal structure.
(3) owing to adopting volcanic cinder as matrix in new packing of the present invention, its selective adsorption and cationic exchange effect can strengthen denitrification ability greatly.There is the very large hole of a lot of internal surface and duct in filler inside of the present invention, and be distributed with positively charged ion in hole, simultaneously part skeleton oxygen also has negative charge, when the duct of inside or hole are once have vacant position, will show the strong magnetism to gas and liquid.Ammonia-state nitrogen larger to polarity especially has very strong selective adsorption effect.In addition, in described method, the aluminium of scoriaceous silicon and interpolation forms aluminosilicate screen work, is easy to carry out ion-exchange with ammonium ion with the positively charged ion of its combination.
(4) new packing of the present invention also can remove the heavy metal ion such as chromium, manganese, zinc, copper in waste water, and the heavy metal ion in waste water and its generation chemical reaction generate oxide compound and precipitation of hydroxide, thus reach removal object.
(5) stearic acid is a kind of saturated fatty acid, is a kind of waxy solid being insoluble in water at normal temperatures, nontoxic, and readily biodegradable, can reduce the oxygen release speed of new packing.
(6) operating performance of the present invention is stablized, and degree affected by environment is little.
Accompanying drawing explanation
Fig. 1 is that the present invention and conventional fillers are to the correlation curve of N2 adsorption ability;
Fig. 2 is that material of the present invention and conventional fillers are to the correlation curve of phosphorus adsorptive power;
Fig. 3 be material oxygen release concentration of the present invention over time.
Embodiment
Below in conjunction with embodiment, the present invention is illustrated.
Embodiment 1
For a preparation method for the filler of artificial swamp water treatment, comprise the following steps:
(1) volcanic cinder mixes with sodium hydroxide, and sode ash mass ratio is 1.0, mixture to be put under retort furnace 500 DEG C of conditions roasting 2 hours, after being cooled to room temperature subsequently, add water after being ground, silica alumina ratio is adjusted to 5, under room temperature condition, be placed on magnetic stirring apparatus, temperature rise to 90 DEG C heating 2 hours, then be warmed up to 95 DEG C heating 2 hours, filter, wash to pH value be 7, put into 80 DEG C, baking oven to dry 4 hours, obtain best nitrogen absorber.
(2) by lanthanum concentration be 0.5% solution ph be adjusted to 10 gradually, according to 1:50(solid-to-liquid ratio) add step 1 prepare best nitrogen absorber, flood more than 16 hours, after filtering, filter cake is in 110 DEG C of oven dry, to be positioned in retort furnace under 450 DEG C of conditions roasting 1 hour, after grinding screening, 120 orders are best nitrogen phosphorus adsorbent.
(3) Wingdale to drop in retort furnace under 800 DEG C of conditions roasting 1 hour, and add water after cooling reaction, then in baking oven, dries the 1 hour water that decrystallizes under 105 DEG C of conditions, soaks, obtain oxygen-release material in input hydrogen peroxide.
(4) be dissolved in tetracol phenixin by a certain amount of stearic acid and Macrogol 4000, stearic acid adding proportion is 0.5%, and heating in water bath makes it dissolve completely to 40 DEG C.The oxygen-release material of preparation in the best nitrogen phosphorus adsorbent then prepared by step 2 and step 3, and quartz sand (increases density of material, be conducive to formed material sedimentation), flyash (shock absorption) adds in proportion, wherein nitrogen phosphorus adsorbent 45%, slow-release oxygen material 35%, stearic acid and Macrogol 4000 mixture 5%, quartz sand 10%, flyash 5%.Be transferred to molding device after abundant stirring, carry out forced air drying after being pressed into different shapes and reclaim tetracol phenixin, the final artificial swamp new packing obtaining synchronous slow oxygen, intensified denitrification and dephosphorization.
The volcanic cinder particle of the Performance of Constructed Wetlands Substrates that the present embodiment is prepared to be particle diameter containing lanthanum ion and calcium peroxide be 5mm, on volcanic cinder particle, the component of loaded article is: nitrogen phosphorus adsorbent 45%, slow-release oxygen material 35%, stearic acid and Macrogol 4000 mixture 5%, quartz sand 10%, flyash 5%.
Embodiment 2
(1) volcanic cinder mixes with sodium hydroxide, and sode ash mass ratio is 1.2, mixture to be put under retort furnace 700 DEG C of conditions roasting 2 hours, after being cooled to room temperature subsequently, add water after being ground, silica alumina ratio is adjusted to 6, under room temperature condition, be placed on magnetic stirring apparatus, temperature rise to 90 DEG C heating 2 hours, then be warmed up to 95 DEG C heating 2 hours, filter, wash to pH value be 7, put into 80 DEG C, baking oven to dry 4 hours, obtain best nitrogen absorber.
(2) by lanthanum concentration be 0.5% solution ph be adjusted to 10 gradually, according to 1:50(solid-to-liquid ratio) add step 1 prepare best nitrogen absorber, flood more than 16 hours, after filtering, filter cake is in 110 DEG C of oven dry, to be positioned in retort furnace under 470 DEG C of conditions roasting 1 hour, after grinding screening, 120 orders are best nitrogen phosphorus adsorbent.
(3) Wingdale to drop in retort furnace under 1000 DEG C of conditions roasting 1 hour, and add water after cooling reaction, then in baking oven, dries the 1 hour water that decrystallizes under 105 DEG C of conditions, soaks, obtain oxygen-release material in input hydrogen peroxide.
(4) be dissolved in tetracol phenixin by a certain amount of stearic acid and Macrogol 4000, stearic acid adding proportion is 1.0%, and heating in water bath makes it dissolve completely to 45 DEG C.The oxygen-release material of preparation in the best nitrogen phosphorus adsorbent then prepared by step 2 and step 3, and quartz sand (increases density of material, be conducive to formed material sedimentation), flyash (shock absorption) adds in proportion, wherein nitrogen phosphorus adsorbent 40%, slow-release oxygen material 30%, stearic acid and Macrogol 4000 mixture 5%, quartz sand 15%, flyash 10%.Be transferred to molding device after abundant stirring, carry out forced air drying after being pressed into different shapes and reclaim tetracol phenixin, the final artificial swamp new packing obtaining synchronous slow oxygen, intensified denitrification and dephosphorization.
The volcanic cinder particle of the Performance of Constructed Wetlands Substrates that the present embodiment is prepared to be particle diameter containing lanthanum ion and calcium peroxide be 10mm, on volcanic cinder particle, the component of loaded article is: nitrogen phosphorus adsorbent 40%, slow-release oxygen material 30%, stearic acid and Macrogol 4000 mixture 5%, quartz sand 15%, flyash 10%.
Embodiment 3
(1) volcanic cinder mixes with sodium hydroxide, and sode ash mass ratio is 1.5, mixture to be put under retort furnace 900 DEG C of conditions roasting 2 hours, after being cooled to room temperature subsequently, add water after being ground, silica alumina ratio is adjusted to 8, under room temperature condition, be placed on magnetic stirring apparatus, temperature rise to 90 DEG C heating 2 hours, then be warmed up to 95 DEG C heating 2 hours, filter, wash to pH value be 7, put into 80 DEG C, baking oven to dry 4 hours, obtain best nitrogen absorber.
(2) by lanthanum concentration be 0.5% solution ph be adjusted to 10 gradually, according to 1:50(solid-to-liquid ratio) add step 1 prepare best nitrogen absorber, flood more than 16 hours, after filtering, filter cake is in 110 DEG C of oven dry, to be positioned in retort furnace under 500 DEG C of conditions roasting 1 hour, after grinding screening, 120 orders are best nitrogen phosphorus adsorbent.
(3) Wingdale to drop in retort furnace under 1200 DEG C of conditions roasting 1 hour, and add water after cooling reaction, then in baking oven, dries the 1 hour water that decrystallizes under 105 DEG C of conditions, soaks, obtain oxygen-release material in input hydrogen peroxide.
(4) be dissolved in tetracol phenixin by a certain amount of stearic acid and Macrogol 4000, stearic acid adding proportion is 1.5%, and heating in water bath makes it dissolve completely to 50 DEG C.The oxygen-release material of preparation in the best nitrogen phosphorus adsorbent then prepared by step 2 and step 3, and quartz sand (increases density of material, be conducive to formed material sedimentation), flyash (shock absorption) adds in proportion, wherein nitrogen phosphorus adsorbent 43%, slow-release oxygen material 32%, stearic acid and Macrogol 4000 mixture 5%, quartz sand 12%, flyash 8%.Be transferred to molding device after abundant stirring, carry out forced air drying after being pressed into different shapes and reclaim tetracol phenixin, the final artificial swamp new packing obtaining synchronous slow oxygen, intensified denitrification and dephosphorization.
The volcanic cinder particle of the Performance of Constructed Wetlands Substrates that the present embodiment is prepared to be particle diameter containing lanthanum ion and calcium peroxide be 15mm, each component of loaded article is: nitrogen phosphorus adsorbent 43%, slow-release oxygen material 32%, stearic acid and Macrogol 4000 mixture 5%, quartz sand 12%, flyash 8%.
As shown in the figure, Fig. 1 is that material of the present invention and volcanic cinder, sand are to the correlation curve of N2 adsorption ability, volcanic cinder, sand and material of the present invention take 8 parts (every part of 10g) respectively and put into Erlenmeyer flask, inject nitrogenous (phosphorus) sewage of different concns, pH value is under 7-8 condition, shake 24 hours in 25 DEG C of water bath with thermostatic control vibrators, after taking out, measure its absorption situation.The adsorptive power of sorbent material represents with adsorptive capacity q:
The adsorptive capacity of wherein q---sorbent material, mg/g;
C
0, C
e---the concentration of phosphorus (nitrogen) in the solution of absorption front and back, mg/L;
V---liquor capacity of getting in adsorption test, ml;
W---adsorbent amount, g.
As shown in Figure 2, Fig. 2 be material of the present invention and volcanic cinder, sand to the correlation curve of phosphorus adsorptive power, adsorption experiment process is the same, measures the situation of its Phosphate Sorption after taking out.
As shown in Figure 3, Fig. 3 be material oxygen release concentration of the present invention over time, a certain amount of material of the present invention is placed in the closed reactor of certain volume, temperature is carry out oxygen release test in the water of 25 DEG C, measures the dissolved oxygen concentration situation over time in water.
Claims (6)
1. for a preparation method for the filler of artificial swamp water treatment, it is characterized in that, comprise the following steps:
Step 1 volcanic cinder and activator mix even, constant-pressure and high-temperature roasting for some time, after being cooled to room temperature, after being ground, add water, regulate silica alumina ratio, under room temperature condition, be placed on magnetic stirring apparatus, temperature rises to 90 DEG C of heating 2 hours, be warmed up to 95 DEG C of heating 2 hours again, filtering, washing to pH value is 7, puts into 80 DEG C, baking oven and dries 4 hours, obtain nitrogen absorber;
Step 2 by lanthanum concentration be 0.5% solution ph be adjusted to 10 gradually, according to solid-liquid mass ratio 1:50, add nitrogen absorber prepared by step 1, flood more than 16 hours, filter after filter cake in 110 DEG C of oven dry, and roasting, grinding sieve obtain nitrogen phosphorus adsorbent; 120 order particle diameter volcanic cinder particles after screening are best nitrogen phosphorus adsorbent;
The roasting under constant-pressure and high-temperature condition of step 3 Wingdale, add water after cooling reaction, dries the water that decrystallizes, and drops in hydrogen peroxide and soak, obtain oxygen-release material;
A certain amount of stearic acid and Macrogol 4000 are dissolved in tetracol phenixin by step 4, heating in water bath makes it dissolve completely, the oxygen-release material of preparation in the nitrogen phosphorus adsorbent then prepared by step 2 and step 3, and quartz sand, flyash by weight percentage example adds, wherein nitrogen phosphorus adsorbent 40-45%, slow-release oxygen material 30-35%, stearic acid and Macrogol 4000 mixture 5%, quartz sand 10-15%, flyash 5-10%, molding device is transferred to after abundant stirring, carry out forced air drying after being pressed into different shapes and reclaim tetracol phenixin, final acquisition synchronous slow oxygen, the Performance of Constructed Wetlands Substrates of intensified denitrification and dephosphorization.
2. method according to claim 1, is characterized in that, in described step 1, activator refers to NaOH, and alkali and scoriaceous mass ratio are 1.0-1.5; Maturing temperature 500-900 DEG C, the time is 1-2 hour; Silica alumina ratio is adjusted to 5-8.
3. method according to claim 1, is characterized in that, in described step 2, maturing temperature is 450-500 DEG C, and the time is 1 hour.
4. method according to claim 1, is characterized in that, in described step 3, maturing temperature is 800-1200 DEG C, and the time is 1 hour; Bake out temperature is 105 DEG C, and the time is 1 hour.
5. method according to claim 1, it is characterized in that, in described step 4, the part by weight of stearic acid and Macrogol 4000 is 1:1, the weight percent of this mixture in tetracol phenixin is 0.5%-1.5%, and the weight percent in final product is 5%; Bath temperature 40-50 DEG C.
6. method according to claim 1, it is characterized in that, in described step 4, the weight percent added to the material component in carbon tetrachloride solution and each component is nitrogen phosphorus adsorbent 40-45%, slow-release oxygen material 30-35%, stearic acid and Macrogol 4000 mixture 5%, quartz sand 10-15%, flyash 5-10%.
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| CN104671425B (en) * | 2015-03-16 | 2017-01-11 | 沈阳环境科学研究院 | Microorganism immobilization method of special filler for artificial wetland |
| CN108178320B (en) * | 2018-01-12 | 2020-06-19 | 南京工业大学 | Microbial fuel cell artificial wetland device and sewage purification method |
| CN111097374B (en) * | 2018-10-25 | 2022-05-06 | 中国科学院生态环境研究中心 | Preparation method of oxygen-carrying and adsorption composite functional material and application of oxygen-carrying and adsorption composite functional material in water body remediation |
| CN111097373B (en) * | 2018-10-25 | 2022-05-06 | 中国科学院生态环境研究中心 | Porous adsorption material and oxygen-carrying and adsorption composite functional material and application thereof |
| CN111559801B (en) * | 2020-05-06 | 2022-08-26 | 中国城市建设研究院有限公司 | Self-oxygen-release filler for repairing black and odorous water body and preparation method and application thereof |
| CN114477355B (en) * | 2022-01-06 | 2023-12-29 | 中国电建集团华东勘测设计研究院有限公司 | Oxygenation and adsorption coupled permeation reaction wall capable of improving river bank pollution cleaning capacity and application |
| CN115465943A (en) * | 2022-09-21 | 2022-12-13 | 王卓 | Constructed wetland nitrogen and phosphorus removal filler with slow-release carbon material and preparation method thereof |
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| JP4119947B2 (en) * | 2001-11-19 | 2008-07-16 | 独立行政法人産業技術総合研究所 | Ceramic porous body and method for producing the same |
| CN100460058C (en) * | 2006-01-20 | 2009-02-11 | 王家强 | Modified natural and self-making floating carrier and mesopore molecular sieve denitrogen dephosphorus material, its preparation and application |
| CN102408151A (en) * | 2011-07-15 | 2012-04-11 | 华东理工大学 | Sedimentary phosphate release inhibitor as well as preparation method and application thereof |
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