CN108970586A - A method of utilizing low-concentration ammonia-nitrogen in biological adsorption removing water body - Google Patents
A method of utilizing low-concentration ammonia-nitrogen in biological adsorption removing water body Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
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- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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Abstract
Present invention relates particularly to a kind of methods using low-concentration ammonia-nitrogen in biological adsorption removing water body；The following steps are included: preparing biomass absorbent agent material first；Then metal ion is supported on biomass absorbent agent material；The adsorbent material is launched into waste water or water body containing ammonia and nitrogen components again, the amino molecule in aqueous medium is fixed on the load biomass absorbent granular materials of metal ion, to realize the adsorbing and removing purification of ammonia and nitrogen components in water body；Adsorbing the ammonia nitrogen molecule to come up can then be desorbed with diluted acid, concentration, be recycled, and sorbent material can be repeated as many times and use；The method of the present invention is easy to operate, is easy to implement, does not have secondary pollution, various raw and auxiliary materials used are cheap to be easy to get, scale is changeable, both it can shed in the water body of large watershed and use, can also be designed to use in special reactor, with its high-efficiency and economic, it is adaptable the features such as and become administer low-concentration ammonia-nitrogen aqueous medium very promising advanced technology.
Description
Technical field
The present invention relates to method for treating water, and in particular to a kind of side using low-concentration ammonia-nitrogen in biological adsorption removing water body
Method.
Background technique
Due to sanitary wastewater, the uncontrolled discharge of industrial wastewater and a large amount of uses of chemical fertilizer, so that the ammonia in natural water
Nitrogen content is generally higher.Ammonia nitrogen is exceeded, and the eutrophication problem that will lead to water body is (as a large amount of in caused water plant, algae and microorganism
Breed and seriously consume the dissolved oxygen in water body), directly influence the benign development of natural ecological environment.Ammonia is to the lethal of fish
Concentration is 0.2~2mg/L, and raiser is to water eutrophication problem very headache.Country has formulated very the discharge of ammonia nitrogen
Stringent control standard, each relevant enterprise also take various suitable methods to the processing of ammonia nitrogen waste water.In general, to super
The ammonia nitrogen waste water (> 10g/L) of high concentration can recycle ammonium salt using evaporative crystallization method；For the ammonia nitrogen waste water of higher concentration
(> 1g/L) can then use air stripping method, the MAP precipitation method, membrane separation process, break point chlorination oxidative treatment；And low concentration
Ammonia nitrogen waste water (< 500mg/L) processing then have ion-exchange, biological denitrificaion method processing.For high-concentration ammonia nitrogenous wastewater,
Processing technique is more mature, and for the ammonia nitrogen waste water or water body purification of low concentration, it is only the difficult point of ammonia nitrogen removal technological development
And challenge.Processing for Low Concentration Ammonia Containing Wastewater, ion-exchange simple process, easy to operate, investment is lower, but resin
Or zeolite quantity is big, difficult for regeneration, costly, and biological denitrificaion rule technical maturity, but long flow path, reactor are big, land occupation
Greatly, often need that additional carbon, energy consumption is high, time-consuming, therefore, there is an urgent need to develop it is more economical, faster, more easily handle it is low dense
Spend the new technology of ammonia nitrogen.
Summary of the invention
The present invention overcomes the shortcomings of the prior art, technical problem to be solved are as follows: provide it is a kind of it is economical, efficiently,
Simply, conveniently, not secondary pollution using biological adsorption removing water body in low-concentration ammonia-nitrogen method.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows:
A method of utilizing low-concentration ammonia-nitrogen in biological adsorption removing water body, comprising the following steps:
A, it is with the biomass material or abandoned biomass rolled into a ball containing carboxyl, sulfydryl, amino or phenolic hydroxyl group active function
Raw material prepares biomass absorbent agent material；
B, biomass absorbent agent material prepared by step a pH value range is added to be 1-14 and contain each metal ion species
Aqueous solution in, carry out metal ion absorption enrichment；The additive amount of the biomass absorbent agent material is every liter to be processed
0.1-50 grams is added in low-concentration ammonia-nitrogen aqueous solution；Stirring 5-1200 minutes, obtains the biomass absorbent for being enriched with metal ion
Agent powder；
C, by the resulting biomass adsorbent powder of step b after water purification is washed 2-3 times repeatedly, in room temperature or 60 DEG C
Hot bellows in be dried to its moisture content be 10-80% when, drying object further grind, sieved and is classified, collection granularity exist
The compound bio adsorbent material that the following particle of 200 mesh can be used as loaded metal ion is spare；
D, the aqueous solution to be processed containing low concentration ammonia nitrogen component is taken, first adjusts its pH value between 6-11, then will
The compound bio adsorbent material investment of the resulting loaded metal ion of step c wherein, stirs, after adsorption reaction 1-10 hours, mistake
Filter separation, detects the ammonia and nitrogen components in water；
E, the resulting adsorbent for having adsorbed amino molecule is filtered in step d to be mixed with the diluted acid that pH value is 2-4, it will be therein
Amino molecule desorption recycling, and the compound bio adsorbent material for having loaded metal ion then continues on for the suction of water body low-concentration ammonia-nitrogen
Attached removing.
Prepared in step a biomass absorbent agent material the specific steps are by biomass material or abandoned biomass with
Alkali, water are stirred hybrid reaction according to the mass ratio of 1:0.05-0.2:0.5-2, stir 12-24 hours, filtering, consolidate
Body product, wherein the alkali be lithium, sodium, potassium, calcium, the oxide of magnesium, hydroxide, carbonate, bicarbonate or ammonium carbonate,
One of ammonium hydrogen carbonate, urea and ammonium hydroxide or two kinds or more mix；The above solid product is washed with water until neutrality, feeding are true
Empty baking oven is 60-120 DEG C of drying in temperature, drying object is smashed, is sieved, the following powder collection of 40 mesh can be used as biomass
Sorbent material.
The biomass material containing carboxyl, sulfydryl, amino, phenolic hydroxyl group active function group is garlic residue, seaweed, wine
Grain, the one or more of tangerine slag, apple skin and chitosan.
Metal ion described in step b is Cu2+、Ni2+、Co2+、Zn2+And Ag+One or more.
Stirring means in step b are mechanical stirring or air stirring, and mixing time is 300-500 minutes.
The present invention is that complexing can occur with ammonia using the basic principle of ammonia nitrogen method in biological adsorption removing water body
Metal ion such as Cu2+、Ni2+、Co2+、Zn2+Or Ag+Deng being supported on biomass absorbent material in advance, then by the adsorption material
The characteristics of material is launched into waste water or water body containing ammonia and nitrogen components, complex reaction can occur with metal ion using amino molecule,
Amino molecule in aqueous medium is fixed on the load biomass absorbent granular materials of metal ion, to realize in water body
The adsorbing and removing of ammonia and nitrogen components purifies；And adsorbing the ammonia nitrogen molecule to come up can then be desorbed with diluted acid, concentration, be recycled, adsorbent
Material can then be repeated as many times and use.
Compared with the prior art, the invention has the following beneficial effects:
The compound bio adsorbent material prepared by the present invention for having loaded metal ion can then be repeated as many times and use.The present invention
Method is easy to operate, process is simple, is easy to implement, does not have secondary pollution, various raw and auxiliary materials used are cheap to be easy to get, scale can be big
Can be small, it can both shed in the water body of large watershed and use, can also be designed to use in special reactor, can both administer
Natural water such as river, lake, cultivation fish pond, can also administer industrial, agricultural, the special of life outlet nitrogen-containing wastewater is controlled
Reason, with its high-efficiency and economic, it is adaptable the features such as and become administer low-concentration ammonia-nitrogen aqueous medium very promising elder generation
Into technology.
Detailed description of the invention
Fig. 1 is the process flow of the biomass adsorbent material processing Low Concentration Ammonia Containing Wastewater of loaded metal ion of the present invention
Figure.
Specific embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
Prepare 10 liters of nitric acid copper ion solution of 0.1M concentration, with the hydrochloric acid and sodium hydroxide solution of 0.1M adjust metal from
After the pH of sub- solution is 6,200 grams of apple skin adsorbent are put into, after being stirred to react 30 minutes, adsorbent is filtered, uses distilled water
After washing 3 times, it is put into hot wind in 60 DEG C of baking oven and dries 6 hours；Further grinding, screening, classification, can be obtained granularity 200
Negative copper biological adsorption powder-product below mesh.10 liters of water samples containing 50mg/L ammonia nitrogen are taken, surveying its pH value is 7.2, is direct plungeed into
The negative copper biological adsorption powder-product of 50 grams of above-mentioned preparations, after being stirred to react 5 hours, it is small to measure ammonia-nitrogen content in water sample for filtering
In 1mg/L.
And absorbent particles are then stirred to react 1 hour with 200 milliliters of dilute hydrochloric acid that pH value is 3, and are constantly added suitable
The hydrochloric acid conditioning solution pH stable of 1:1 volume ratio is 3, then is filtered, and filtered ammonia nitrogen in solution concentration is 25g/L,
It is 1 that its pH value, which can further be adjusted, and obtains solid ammonium chloride using evaporative crystallization method concentration and recovery.Absorbent particles then return
It goes to reuse.
Embodiment 2
Prepare 10 liters of nickel nitrate solion of 0.1M concentration, with the hydrochloric acid and sodium hydroxide solution of 0.1M adjust metal from
After the pH of sub- solution is 6,100 grams of Cortex Bulbus Allii adsorbent are put into, after being stirred to react 300 minutes, adsorbent is filtered, uses distilled water
After washing 3 times, it is put into hot wind in 60 DEG C of baking oven and dries 6 hours；Further grinding, screening, classification, can be obtained granularity 200
Negative nickel biological adsorption powder-product below mesh.10 liters of water samples containing 50mg/L ammonia nitrogen are taken, surveying its pH value is 7.2, is direct plungeed into
The negative nickel biological adsorption powder-product of 50 grams of above-mentioned preparations, after being stirred to react 5 hours, it is small to measure ammonia-nitrogen content in water sample for filtering
In 3mg/L.
And absorbent particles are then stirred to react 1 hour with 200 milliliters of dilute hydrochloric acid that pH value is 3, and are constantly added suitable
The hydrochloric acid conditioning solution pH stable of 1:1 volume ratio is 3, then is filtered, and filtered ammonia nitrogen in solution concentration is 24g/L,
It is 1 that its pH value, which can further be adjusted, and obtains solid ammonium chloride using evaporative crystallization method concentration and recovery.Absorbent particles then return
It goes to reuse.
Embodiment 3
Prepare 10 liters of nitric acid silver ion solution of 0.1M concentration, with the nitric acid and sodium hydroxide solution of 0.1M adjust metal from
After the pH of sub- solution is 4,300 grams of beer malt vinasse adsorbent is put into, after being stirred to react 500 minutes, adsorbent is filtered, used
After distillation water washing 3 times, it is put into hot wind in 60 DEG C of baking oven and dries 6 hours；Further grinding, screening, classification, can be obtained granularity
Silver biological adsorption powder-product is born below 200 mesh.10 liters of water samples containing 50mg/L ammonia nitrogen are taken, surveying its pH value is 7.2, directly
The negative silver-colored biological adsorption powder-product of 50 grams of above-mentioned preparations of investment, after being stirred to react 5 hours, filtering measures ammonia nitrogen in water sample and contains
Amount is less than 0.5mg/L.
And absorbent particles are then stirred to react 1 hour with 200 milliliters of dilute citric acid that pH value is 4, then are filtered, and are filtered
Ammonia nitrogen in solution concentration afterwards is 24g/L, and can further adjust its pH value is 1, and is obtained using evaporative crystallization method concentration and recovery
Solid citric acid ammonium.Absorbent particles then return to reuse.
Embodiment 4
Prepare 10 liters of zinc nitrate solion of 0.1M concentration, with the hydrochloric acid and sodium hydroxide solution of 0.1M adjust metal from
After the pH of sub- solution is 6,200 grams of Cortex Bulbus Allii adsorbent are put into, after being stirred to react 30 minutes, adsorbent is filtered, uses distilled water
After washing 3 times, it is put into hot wind in 60 DEG C of baking oven and dries 6 hours；Further grinding, screening, classification, can be obtained granularity 200
Negative zinc biological adsorption powder-product below mesh.10 liters of water samples containing 20mg/L ammonia nitrogen are taken, surveying its pH value is 9.9, then directly throws
Enter 50 grams or more the negative zinc biological adsorption powder-products respectively prepared, after being stirred to react 5 hours, filtering measures ammonia nitrogen in water sample and contains
Amount is less than 1mg/L.
And absorbent particles are then stirred to react 1 hour with 200 milliliters of dilute hydrochloric acid that pH value is 3, and are constantly added suitable
The hydrochloric acid conditioning solution pH stable of 1:1 volume ratio is 3, then is filtered, and filtered ammonia nitrogen in solution concentration is 10g/L,
It is 1 that its pH value, which can further be adjusted, and obtains solid ammonium chloride using evaporative crystallization method concentration and recovery.Absorbent particles then return
It goes to reuse.
Embodiment 5
10 liters of certain waterworks water sample is taken, chemically examining ammonia nitrogen concentration therein is 10mg/L, and pH value 7.8 puts into embodiment party
50 grams of negative copper biological adsorption material prepared in formula 1, after being stirred to react 5 hours, filtering measures ammonia-nitrogen content in water sample and is less than
1mg/L。
And absorbent particles are then stirred to react 1 hour with 200 milliliters of dilute hydrochloric acid that pH value is 3, and are constantly added suitable
The hydrochloric acid conditioning solution pH stable of 1:1 volume ratio is 3, then is filtered, and filtered ammonia nitrogen in solution concentration is 4.5g/L,
It is 1 that its pH value, which can further be adjusted, and obtains solid ammonium chloride using evaporative crystallization method concentration and recovery.Absorbent particles then return
It goes to reuse.
Embodiment 6
Prepare 0.1M concentration copper nitrate and 10 liters of zinc nitrate mixed solution, with the hydrochloric acid and sodium hydroxide solution tune of 0.1M
After the pH for saving metal ion solution is 6, apple skin and 200 grams of Cortex Bulbus Allii mixed adsorbent are put into, it, will after being stirred to react 30 minutes
Adsorbent filtering after being washed with distilled water 3 times, is put into hot wind in 60 DEG C of baking oven and dries 6 hours；It further grinds, screening, divide
Grade, can be obtained the biological adsorption powder-product of granularity negative copper zinc below 200 mesh.Take 10 liters of water containing 50mg/L ammonia nitrogen
Sample, surveying its pH value is 7.2, direct plunges into the biological adsorption powder-product of the negative copper zinc of 50 grams of above-mentioned preparations, is stirred to react 5 hours
Afterwards, it filters, measures ammonia-nitrogen content in water sample and be less than 1mg/L.
And absorbent particles are then stirred to react 1 hour with 200 milliliters of dilute hydrochloric acid that pH value is 3, and are constantly added suitable
The hydrochloric acid conditioning solution pH stable of 1:1 volume ratio is 3, then is filtered, and filtered ammonia nitrogen in solution concentration is 20g/L,
It is 1 that its pH value, which can further be adjusted, and obtains solid ammonium chloride using evaporative crystallization method concentration and recovery.Absorbent particles then return
It goes to reuse.
Above case study on implementation is to help those skilled in the art and more fully understands core of the invention skill
Art main points, all known biology to metal ion with absorption property that can be detailed of the those of ordinary skill including biological adsorption field
Adsorbent is raw material, carries out and prepares the suction of metal load type biomass to the adsorption operations of the metal cations such as copper, silver, nickel, cobalt, zinc
Enclosure material.Biomass absorbent material therein refers to the metal cations such as all pairs of copper, silver, nickel, cobalt, zinc with adsorption effect
Biomass material sorbent material；The waste water containing ammonia nitrogen in embodiments herein is either the ammonia nitrogen mould manually prepared
Quasi- waste water, the water sample being also possible in the industrial wastewater or natural environment containing ammonia nitrogen that actual industry spot is fetched.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (5)
1. a kind of method using low-concentration ammonia-nitrogen in biological adsorption removing water body, which comprises the following steps:
A, using the biomass material or abandoned biomass rolled into a ball containing carboxyl, sulfydryl, amino or phenolic hydroxyl group active function as raw material,
Prepare biomass absorbent agent material；
B, biomass absorbent agent material prepared by step a is added to the water that pH value range is 1-14 and contains each metal ion species
In solution, the absorption enrichment of metal ion is carried out；The additive amount of the biomass absorbent agent material is every liter to be processed low dense
It spends and adds 0.1-50 grams in ammonia nitrogen aqueous solution；Stirring 5-1200 minutes, obtains the biomass adsorbent powder for being enriched with metal ion
End；
C, by the resulting biomass adsorbent powder of step b after water purification is washed 2-3 times repeatedly, in room temperature or 60 DEG C of heat
Be dried in bellows its moisture content be 10-80% when, drying object further grind, sieved and is classified, collection granularity in 200 mesh
The compound bio adsorbent material that following particle can be used as loaded metal ion is spare；
D, the aqueous solution to be processed containing low concentration ammonia nitrogen component is taken, first adjusts its pH value between 6-11, then by step c
The compound bio adsorbent material investment of resulting loaded metal ion wherein, after adsorption reaction 1-10 hours, filter and divide by stirring
From, detect water in ammonia and nitrogen components；
E, the resulting adsorbent for having adsorbed amino molecule is filtered in step d and is mixed with the diluted acid that pH value is 2-4, by ammonia therein point
Subsolution sucks back receipts, and the absorption that the compound bio adsorbent material for having loaded metal ion then continues on for water body low-concentration ammonia-nitrogen is de-
It removes.
2. a kind of method using low-concentration ammonia-nitrogen in biological adsorption removing water body according to claim 1, feature exist
In, prepared in step a biomass absorbent agent material the specific steps are by biomass material or abandoned biomass and alkali, water by
It is stirred hybrid reaction according to the mass ratio of 1:0.05-0.2:0.5-2, is stirred 12-24 hours, filtering obtains solid product,
Wherein, the alkali be lithium, sodium, potassium, calcium, the oxide of magnesium, hydroxide, carbonate, bicarbonate, ammonium carbonate, ammonium hydrogen carbonate,
One of urea and ammonium hydroxide or two kinds or more mix；The above solid product is washed with water up to neutrality, is sent into vacuum drying oven,
Temperature is 60-120 DEG C of drying, and drying object is smashed, is sieved, the following powder collection of 40 mesh can be used as biomass adsorbent material
Material.
3. a kind of method using low-concentration ammonia-nitrogen in biological adsorption removing water body according to claim 1, feature exist
In the biomass material containing carboxyl, sulfydryl, amino or phenolic hydroxyl group active function group in step a is garlic residue, sea
Algae, vinasse, tangerine slag, apple skin and chitosan one or more.
4. a kind of method using low-concentration ammonia-nitrogen in biological adsorption removing water body according to claim 1, feature exist
In metal ion described in step b is Cu2+、Ni2+、Co2+、Zn2+And Ag+One or more.
5. a kind of method using low-concentration ammonia-nitrogen in biological adsorption removing water body according to claim 1, feature exist
In the stirring means in step b are mechanical stirring or air stirring, and mixing time is 300-500 minutes.
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Cited By (2)
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| CN110357198A (en) * | 2019-06-11 | 2019-10-22 | 武汉兴天宇环境股份有限公司 | A kind of adsorbent material and preparation method thereof for Low Concentration Ammonia Containing Wastewater processing |
| CN115872486A (en) * | 2022-12-28 | 2023-03-31 | 江西省水利科学院 | Device and method for removing trace antibiotics in sewage through enrichment and oxidation |
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Application publication date: 20181211 |