CN106669621A - Preparation method and application of chitosan/zeolite molecular sieve adsorbent - Google Patents

Preparation method and application of chitosan/zeolite molecular sieve adsorbent Download PDF

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CN106669621A
CN106669621A CN201710034604.1A CN201710034604A CN106669621A CN 106669621 A CN106669621 A CN 106669621A CN 201710034604 A CN201710034604 A CN 201710034604A CN 106669621 A CN106669621 A CN 106669621A
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shitosan
water
nitrogen
molecular sieve
chitosan
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CN106669621B (en
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郜玉楠
孙美乔
王信之
周东旭
周历涛
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Shenyang Jianzhu University
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Shenyang Jianzhu University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The invention belongs to the technical field of water treatment, and particularly relates to a preparation method and application of chitosan/zeolite molecular sieve adsorbent. The preparation method comprises the following steps: adding chitosan into an acetic acid solution to prepare a chitosan acetic acid solution having a mass concentration of 1.8-2.2 percent, soaking a zeolite molecular sieve in the chitosan acetic acid solution, washing and drying to form chitosan/zeolite molecular sieve adsorbent particles; and purifying 3-nitrogen pollutant-containing raw water by using the chitosan/zeolite molecular sieve adsorbent particles as a filter material of a rapid filter to filter and remove ammonia-nitrogen, nitrate nitrogen and nitrite nitrogen in water, wherein the range of ammonia-nitrogen removal rate is 70-85 percent, the range of nitrate nitrogen removal rate is 55-80 percent, and the range of nitrite nitrogen removal rate is 30-40 percent. The preparation method has the advantages of low investment cost, good operation effect, long regeneration cycle, recycling availability and small environmental factor influence, and is suitable for transformation of large water works and application of small-scale integrated equipment.

Description

A kind of preparation method and application of shitosan/zeolite adsorbent
Technical field
The invention belongs to water-treatment technology field, and in particular to a kind of preparation side of shitosan/zeolite adsorbent Method and application.
Background technology
Due to the continuous development of industrial and agricultural production, cause the surface water and groundwater drinking water source of China's most area It is heavily contaminated, wherein three polluted by nitrogen are main problems, including ammonia nitrogen（NH4 +-N）, nitrate nitrogen（NO3 --N）, nitrous acid Salt nitrogen（NO2 --N）Pollutant, these three materials are referred to as " three nitrogen ".When three polluted by nitrogen is contained in water, can be to environment and biology Serious harm is caused, ammonia nitrogen can easily produce nitrite nitrogen in processing procedure in water, and nitrite nitrogen meeting and human body Protein produce carcinogenic nitrosamine, the water of long-term drink nitrite nitrogen is very big to harm, nitrate and nitrous acid Salt can form stable, carcinogenic and mutagenicity N-nitrosamine and nitroso-group under the effect of various organic compounds containing nitrogens The various N- nitroso-groups compounds of group of amide, and by destroy cell and tissue breathing, cause lactic acid in blood, cholesterol and Leukocyte increases, and protein is reduced in a large number, so as to cause various diseases.
China《Drinking water sanitary standard》（GB5749-2006）Ammonia nitrogen, nitrate, nitrite are proposed tighter The requirement of lattice, respectively provided ammonia nitrogen limit value be 0.5mg/L, the nitrate limit value with surface water as water source be 10mg/L, with Subsoil water is 20mg/L for the nitrate limit value at water source, and the limit value of nitrite is 1.0mg/L, and water treatment plant of China generally adopts Common process, i.e. " coagulation-precipitation-filtration-sterilization ", the technique is poor for the removal ability of three nitrogen.If in Water purification Three nitrogen pollutants can not be effectively removed in technique, may cause that Biological Stability in Drinking Water is poor, pathogenic risk is larger etc. asks Topic.
Shitosan（CTS）It is a kind of natural flocculating agent, it is widely present in Crustacean, due in its molecular structure Containing substantial amounts of amino and hydroxyl isoreactivity group, property is more active, can modify, activates and be coupled, therefore can occur various Chemical modification, and can couple to form multifunctional composite with adsorbing material, coagulant, microorganism etc., in water process especially It is that drinking water treatment field has quite wide application prospect.
Zeolite molecular sieve is the hydrate of crystalline alumino slaine, and after activation, hydrone is removed, remaining atom Cage structure is formed, makes zeolite molecular sieve that there is uniform bore road, its aperture is suitable with general molecular size, because molecular sieve can be by The Molecular Adsorption less than its aperture the molecular repulsion bigger than aperture outside its hole, plays screening molecule to inside hole Effect, therefore molecular sieve of gaining the name.Zeolite molecular sieve can adsorb the ammonia nitrogen in water and nitrate nitrogen equimolecular, and it has unique suction Attached property, ion exchangeable, because zeolite molecular sieve synthesis material is abundant, synthesis condition is simple, reproducible utilization is strong, so tool There is good application potential.
At present, application of the ultrafiltration in drinking water treatment field is more and more extensive, reaches as motive force by using differential static pressure To separating effect, so as to go eliminating water in the polluter such as turbidity, microorganism, colloid, but the aperture of ultrafilter membrane is generally less than 0.01um, it is poor to the removal ability of ammonia nitrogen, nitrate nitrogen, small organic molecule, therefore ultrafiltration needs and other process combination Can be only achieved the purpose for improving effluent quality.Common ultrafiltration pretreatment technique mainly includes absorption method, oxidizing process, Coagulation Method Deng.
The content of the invention
For the pollution problem that there are three nitrogen in drinking water, the present invention provides a kind of shitosan/zeolite adsorbent Preparation method and application, it is therefore an objective to the existing conventional treatment process of solution goes to ammonia nitrogen, nitrate nitrogen, nitrite nitrogen in water The poor problem of removing solid capacity.
The preparation method of the shitosan/zeolite adsorbent of the present invention, follows the steps below：
（1）During shitosan is added into volume fraction for 0.8% ~ 1.2% acetum, mass concentration 1.8% ~ 2.2% is configured to Chitosan-acetic acid solution；
（2）Zeolite molecular sieve is added to into step（1）In chitosan-acetic acid solution in soak, the time is 8-12h, after by granule Take out, deionized water is rinsed until washing liquid is neutrality, after be placed in heating 5-8h in 60-80 DEG C of drying baker, form shitosan/boiling Stone adsorbent of molecular sieve granule.
Wherein, described deacetylating degree of chitosan >=85%, zeolite molecules mesh size is 4A.
The application of the shitosan/zeolite adsorbent of the present invention is followed the steps below：
（1）Using shitosan/zeolite adsorbent granule as rapid filter filtrate, in rapid filter filtrate upper strata be shitosan/ Zeolite molecular sieve adsorption particle, particle diameter is 0.3-0.5cm, filtrate 1.2 ~ 1.5m of height, and lower floor is quartz sand filter media, and particle diameter is 0.1-0.2cm, filtrate is highly 0.3m, and filter tank average rate of filtering is 5 ~ 6m/h；
（2）The water inlet end of rapid filter is connected with tube settler, and tube settler water inlet end is connected with mechanic whirl-nett reaction pond, machine Tool agitating reaction pond water inlet end is connected with pipe-line mixer, and the raw water containing three nitrogen pollutants, rapid filter are passed through in pipe-line mixer Water side be connected with ultrafiltration membrane pool；
（3）Raw water containing three nitrogen pollutants is sufficiently mixed through pipe-line mixer with coagulant, in mechanic whirl-nett reaction pond Middle formation flco, after complete mud-water separation in sedimentation tank, water outlet enters shitosan/zeolite molecular sieve adsorption particle rapid filter, Ammonia nitrogen in eliminating water, nitrate nitrogen, nitrite nitrogen are removed in filtration, be 70%-85% to the clearance scope of ammonia nitrogen, and nitrate nitrogen goes Removal frequency range is 55% ~ 80%, and the clearance scope of cultured water is 30%-40%, afterwards into ultrafiltration membrane pool, in further going eliminating water Turbidity and Organic substance.
Wherein, described rapid filter is provided with overfall and backwash water inlet, and backwashing period is 24-36h, regeneration week Phase 1-2, by the way of concentration 3-4g/L sodium hydroxide solution immersion filtering material particle, soak time is 6-8h to regenerative process.
Described hyperfiltration membrane assembly is immersion type membrane component, and kit form is hollow-fibre membrane or Flat Membrane, and material is Polrvinyl chloride or Kynoar, ultrafilter membrane pore diameter range is that between 0.01-0.05um, ultrafiltration membrane flux is 30-70L/m2H, Hydraulic detention time is 10-30min, and the ultrafilter membrane physical cleaning cycle is 30-40min, and maintainability Chemical cleaning is from concentration The liquor natrii hypochloritises of 400mg/L, the cleaning frequency is 4-5d, and soak time is 80min, and the offline property Chemical cleaning cycle is 4-6 Individual month, successively using concentration 2g/L soaking with sodium hydroxide 2h, the soak with hydrochloric acid 5h of concentration 5g/L.
Described go ammonia nitrogen in eliminating water, nitrate nitrogen, the range of reaction temperature of nitrite nitrogen is 10-30 DEG C.
In described raw water ammonia nitrogen pollutant content be 2-5mg/L, nitrate pollutants content be 20-30mg/L, nitrous Hydrochlorate pollutant load is 1.0-1.2mg/L.
Compared with prior art, of the invention the characteristics of and beneficial effect are：
（1）Shitosan/zeolite adsorbent prepared by the present invention is a kind of graininess water treatment agent, with the micro- dirt of removal Ammonia nitrogen in dye water, nitrate nitrogen, the efficiency of nitrite nitrogen, because shitosan is by the polymer of natural organic-compound extraction Matter, zeolite molecular sieve is a kind of abundant alkali alumino-silicates of synthesis material, so shitosan/zeolite molecules prepared by the present invention Sieve is a kind of environmentally friendly water treatment absorbent.Shitosan/zeolite adsorbent is using the activity on shitosan surface Group and nitrate nitrogen, nitrite nitrogen reaction, adsorb ammonia nitrogen, so as to reach simultaneously by the uniform duct of zeolite molecular sieve Ammonia nitrogen in eliminating water, nitrate nitrogen, the effect of nitrite nitrogen is gone to make up current water factory and use conventional water treatment medicament to containing three nitrogen The problem of Pollutant Treatment effect difference.
（2）Shitosan/zeolite adsorbent filtrate that the present invention is adopted carries out drainage with reference to ultrafiltration technology, with tradition Water factory's " coagulation-precipitation-filtration-sterilization " technique is compared, the raw water after shitosan/zeolite adsorbent process, and three The treatment effect of nitrogen pollutant is more preferable so that nitrogen-containing pollutant concentration is reduced in ultrafiltration membrane pool, the outlet effect after ultrafiltration More preferably.
（3）Cost of investment of the present invention is low, operational effect is good, regeneration period length, recoverable, by such environmental effects It is little, it is adaptable to which that Large Water Works are transformed, and the application of small-scale integration apparatus.
Description of the drawings
Fig. 1 is that shitosan/zeolitic molecular sieve particle picture is prepared in embodiment 1；
Fig. 2 is the rapid filter installation drawing in the embodiment of the present invention with shitosan/zeolite molecular sieve adsorption particle as filtrate；
Wherein：1：Water inlet；2：Shitosan/zeolite molecular sieve adsorption particle filtrate；3：Quartz sand filter media；4：Overfall； 5：Go out Water；6：Backwash is intake；
Fig. 3 is the overall flow figure of the application of shitosan/zeolite adsorbent in the embodiment of the present invention；
Wherein：7：Pipe-line mixer；8：Mechanic whirl-nett reaction pond；9：Tube settler；10：Shitosan/zeolitic molecular sieve particle Rapid filter；11：Ultrafiltration membrane pool；12：Backwash water pipe；13：Draining discharge pipeline.
Fig. 4 is that shitosan in embodiment 1/zeolite molecular sieve adsorption particle rapid filter is contrasted to the clearance of three nitrogen pollutants Figure.
Specific embodiment
Following specific embodiments are that present invention is further illustrated, but the flesh and blood of the present invention and are not only limited In described in following specific embodiments, combination in any between any specific embodiment and the simple change to preparation process belong to In protection domain of the presently claimed invention.
Embodiment 1
The preparation method of the shitosan/zeolite adsorbent of the present embodiment is followed the steps below：
（1）The shitosan of deacetylation 85% is added in the acetum of volume fraction 0.8%, mass concentration 1.8% is configured to Chitosan-acetic acid solution；
（2）Zeolite molecular sieve of the aperture for 4A is added to into step（1）In chitosan-acetic acid solution in soak, the time is 10h, Granule is taken out afterwards, deionized water is rinsed until washing liquid is neutrality, after be placed in heating 6h in 70 DEG C of drying baker, form shell and gather Sugar/zeolite molecular sieve adsorption particle, as shown in Figure 1.
The shitosan of the present embodiment/zeolite adsorbent granule removes nitrate, nitrite nitrogen, ammonia nitrogen pollutant Application, as shown in Figures 2 and 3, follow the steps below：
（1）Using shitosan/zeolite adsorbent granule as rapid filter filtrate, in rapid filter filtrate upper strata be shitosan/ Zeolite molecular sieve adsorption particle, particle diameter is 0.3-0.5cm, and filtrate height 1.2m, lower floor is quartz sand filter media, and particle diameter is 0.1- 0.2cm, filtrate is highly 0.3m, and filter tank average rate of filtering is 5.5m/h, and backwashing period is 36h；
（2）The water inlet end of rapid filter is connected with tube settler, and tube settler water inlet end is connected with mechanic whirl-nett reaction pond, machine Tool agitating reaction pond water inlet end is connected with pipe-line mixer, and the raw water containing three nitrogen pollutants, rapid filter are passed through in pipe-line mixer Water side be connected with ultrafiltration membrane pool；
（3）Raw water containing three nitrogen pollutants is sufficiently mixed through pipe-line mixer with coagulant, in mechanic whirl-nett reaction pond Middle formation flco, after complete mud-water separation in sedimentation tank, water outlet enters shitosan/zeolite molecular sieve adsorption particle rapid filter, Ammonia nitrogen in eliminating water, nitrate nitrogen, nitrite nitrogen are removed in filtration, and in operation a cycle, the average removal rate of ammonia nitrogen is 71.06%, The average removal rate of nitrate is 76.07%, and the average removal rate of nitrite nitrogen is 35.23%, and range of reaction temperature is 20 DEG C, after Into ultrafiltration membrane pool, turbidity and Organic substance in eliminating water are further removed.
Ammonia nitrogen pollutant mean concentration is 3.49mg/L in described raw water, and nitrate pollutants mean concentration is 28.67mg/L, nitrite pollution thing mean concentration is 1.05mg/L, as shown in Figure 4.
Embodiment 2
The preparation method of the shitosan/zeolite adsorbent of the present embodiment is followed the steps below：
（1）The shitosan of deacetylation 90% is added in the acetum of volume fraction 1%, the shell for being configured to mass concentration 2% gathers Sweet and sour acid solution；
（2）Zeolite molecular sieve of the aperture for 4A is added to into step（1）In chitosan-acetic acid solution in soak, the time is 12h, Granule is taken out afterwards, deionized water is rinsed until washing liquid is neutrality, after be placed in heating 8h in 80 DEG C of drying baker, form shell and gather Sugar/zeolite molecular sieve adsorption particle.
The shitosan of the present embodiment/zeolite adsorbent granule removes nitrate, nitrite nitrogen, ammonia nitrogen pollutant Application, as shown in Figures 2 and 3, follow the steps below：
（1）Using shitosan/zeolite adsorbent granule as rapid filter filtrate, in rapid filter filtrate upper strata be shitosan/ Zeolite molecular sieve adsorption particle, particle diameter is 0.3-0.5cm, and filtrate height 1.5m, lower floor is quartz sand filter media, and particle diameter is 0.1- 0.2cm, filtrate is highly 0.3m, and filter tank average rate of filtering is 6m/h, and backwashing period is 36h, and backwash is using washing, intensity 15 L/(s·m2), washing time is 10min；
（2）The water inlet end of rapid filter is connected with tube settler, and tube settler water inlet end is connected with mechanic whirl-nett reaction pond, machine Tool agitating reaction pond water inlet end is connected with pipe-line mixer, and the raw water containing three nitrogen pollutants, rapid filter are passed through in pipe-line mixer Water side be connected with ultrafiltration membrane pool；
（3）Raw water containing three nitrogen pollutants is sufficiently mixed through pipe-line mixer with coagulant, in mechanic whirl-nett reaction pond Middle formation flco, after complete mud-water separation in sedimentation tank, water outlet enters shitosan/zeolite molecular sieve adsorption particle rapid filter, Ammonia nitrogen in eliminating water, nitrate nitrogen, nitrite nitrogen are removed in filtration, run half a year, are 85% to the clearance of ammonia nitrogen, nitrate nitrogen Clearance is 79.6%, and the clearance of nitrite nitrogen is 36%, and 10 DEG C of reaction temperature, afterwards into ultrafiltration membrane pool, is further removed Turbidity and Organic substance in water, the clearance of turbidity is 95%, and the clearance of permanganate index is 85.8%.
Wherein, in described raw water ammonia nitrogen pollutant content be 5mg/L, nitrate pollutants content be 22mg/L, nitrous Hydrochlorate pollutant load is 1.2mg/L, and turbidity is 1.5NTU, and permanganate index is 2.5mg/L.
Embodiment 3
The preparation method of the shitosan/zeolite adsorbent of the present embodiment is followed the steps below：
（1）The shitosan of deacetylation 95% is added in the acetum of volume fraction 1.2%, mass concentration 2.2% is configured to Chitosan-acetic acid solution；
（2）Zeolite molecular sieve of the aperture for 4A is added to into step（1）In chitosan-acetic acid solution in soak, the time is 8h, Granule is taken out afterwards, deionized water is rinsed until washing liquid is neutrality, after be placed in heating 6h in 60 DEG C of drying baker, form shell and gather Sugar/zeolite molecular sieve adsorption particle.
The shitosan of the present embodiment/zeolite adsorbent granule removes nitrate, nitrite nitrogen, ammonia nitrogen pollutant Application, as shown in Figures 2 and 3, follow the steps below：
（1）Using shitosan/zeolite adsorbent granule as rapid filter filtrate, in rapid filter filtrate upper strata be shitosan/ Zeolite molecular sieve adsorption particle, particle diameter is 0.3-0.5cm, and filtrate height 1.5m, lower floor is quartz sand filter media, and particle diameter is 0.1- 0.2cm, filtrate is highly 0.3m, and filter tank average rate of filtering is 6m/h, and backwashing period is 36h, and backwash is using washing, intensity 15 L/(s·m2), washing time is 10min；
（2）The water inlet end of rapid filter is connected with tube settler, and tube settler water inlet end is connected with mechanic whirl-nett reaction pond, machine Tool agitating reaction pond water inlet end is connected with pipe-line mixer, and the raw water containing three nitrogen pollutants, rapid filter are passed through in pipe-line mixer Water side be connected with ultrafiltration membrane pool；
（3）Raw water containing three nitrogen pollutants is sufficiently mixed through pipe-line mixer with coagulant, in mechanic whirl-nett reaction pond Middle formation flco, after complete mud-water separation in sedimentation tank, water outlet enters shitosan/zeolite molecular sieve adsorption particle rapid filter, Ammonia nitrogen in eliminating water, nitrate nitrogen, nitrite nitrogen are removed in filtration, are run 1.5 years, carry out shitosan/zeolite molecular sieve adsorption particle Regeneration, regenerative process adopts sodium hydroxide solution（4g/L）The mode of immersion granule, soak time is 8h.After regeneration, ammonia nitrogen Clearance be 72.5%, the average removal rate of nitrate is 65.8%, and the average removal rate of nitrite nitrogen is 36.8%, reaction temperature Degree scope is 25 DEG C, afterwards into ultrafiltration membrane pool, further removes turbidity and Organic substance in eliminating water.
Wherein, in described water sample ammonia nitrogen pollutant mean concentration be 2.58mg/L, nitrate pollutants mean concentration For 22.6mg/L, nitrite pollution thing mean concentration is 1.15mg/L.
The application and regeneration of the shitosan/zeolite adsorbent of the present embodiment, illustrates the shitosan/zeolite molecular sieve Adsorbent agent can replace original common process filter, for processing water in three nitrogen pollutants, and regeneration effect is preferably, It is still higher to three nitrogen pollutant clearances after regeneration.

Claims (7)

1. a kind of preparation method of shitosan/zeolite adsorbent, it is characterised in that follow the steps below：
（1）During shitosan is added into volume fraction for 0.8% ~ 1.2% acetum, mass concentration 1.8% ~ 2.2% is configured to Chitosan-acetic acid solution；
（2）Zeolite molecular sieve is added to into step（1）In chitosan-acetic acid solution in soak, the time is 8-12h, after by granule Take out, deionized water is rinsed until washing liquid is neutrality, after be placed in heating 5-8h in 60-80 DEG C of drying baker, form shitosan/boiling Stone adsorbent of molecular sieve granule.
2. the preparation method of a kind of shitosan/zeolite adsorbent according to claim 1, it is characterised in that described Deacetylating degree of chitosan >=85%, zeolite molecules mesh size be 4A.
3. the application of shitosan/zeolite adsorbent as claimed in claim 1, it is characterised in that enter according to following steps OK：
（1）Using shitosan/zeolite adsorbent granule as rapid filter filtrate, in rapid filter filtrate upper strata be shitosan/ Zeolite molecular sieve adsorption particle, particle diameter is 0.3-0.5cm, filtrate 1.2 ~ 1.5m of height, and lower floor is quartz sand filter media, and particle diameter is 0.1-0.2cm, filtrate is highly 0.3m, and filter tank average rate of filtering is 5 ~ 6m/h；
（2）The water inlet end of rapid filter is connected with tube settler, and tube settler water inlet end is connected with mechanic whirl-nett reaction pond, machine Tool agitating reaction pond water inlet end is connected with pipe-line mixer, and the raw water containing three nitrogen pollutants, rapid filter are passed through in pipe-line mixer Water side be connected with ultrafiltration membrane pool；
（3）Raw water containing three nitrogen pollutants is sufficiently mixed through pipe-line mixer with coagulant, in mechanic whirl-nett reaction pond Middle formation flco, after complete mud-water separation in sedimentation tank, water outlet enters shitosan/zeolite molecular sieve adsorption particle rapid filter, Ammonia nitrogen in eliminating water, nitrate nitrogen, nitrite nitrogen are removed in filtration, be 70%-85% to the clearance scope of ammonia nitrogen, and nitrate nitrogen goes Removal frequency range is 55% ~ 80%, and the clearance scope of cultured water is 30%-40%, afterwards into ultrafiltration membrane pool, in further going eliminating water Turbidity and Organic substance.
4. the application of a kind of shitosan/zeolite adsorbent according to claim 3, it is characterised in that described is fast Filter tank is provided with overfall and backwash water inlet, and backwashing period is 24-36h, and regeneration period 1-2, regenerative process is adopted Concentration 3-4g/L sodium hydroxide solution soaks the mode of filtering material particle, and soak time is 6-8h.
5. the application of a kind of shitosan/zeolite adsorbent according to claim 3, it is characterised in that described is super Filter membrane component is immersion type membrane component, and kit form is hollow-fibre membrane or Flat Membrane, and material is polrvinyl chloride or gathers inclined fluorine Ethylene, ultrafilter membrane pore diameter range is that between 0.01-0.05um, ultrafiltration membrane flux is 30-70L/m2H, hydraulic detention time is 10-30min, the ultrafilter membrane physical cleaning cycle is 30-40min, and maintainability Chemical cleaning is from the hypochlorous acid that concentration is 400mg/L Sodium solution, the cleaning frequency is 4-5d, and soak time is 80min, and the offline property Chemical cleaning cycle is 4-6 month, successively using dense Degree 2g/L soaking with sodium hydroxide 2h, the soak with hydrochloric acid 5h of concentration 5g/L.
6. the application of a kind of shitosan/zeolite adsorbent according to claim 3, it is characterised in that described goes Ammonia nitrogen, nitrate nitrogen, the range of reaction temperature of nitrite nitrogen are 10-30 DEG C in eliminating water.
7. a kind of application of shitosan/zeolite adsorbent according to claim 3, it is characterised in that described original Ammonia nitrogen pollutant content is 2-5mg/L in water, and nitrate pollutants content is 20-30mg/L, and nitrite pollution thing content is 1.0-1.2mg/L。
CN201710034604.1A 2017-01-18 2017-01-18 A kind of preparation method and application of chitosan/zeolite adsorbent Active CN106669621B (en)

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CN107398257A (en) * 2017-09-26 2017-11-28 沈阳建筑大学 A kind of preparation method and application of modified zeolite molecular sieve adsorption particle
CN107893345A (en) * 2017-11-10 2018-04-10 安徽同利塑胶彩印有限公司 A kind of preparation method of food paper-plastic package material
CN109516522A (en) * 2018-12-12 2019-03-26 黄舰 A kind of application of organic inorganic hybridization zeolite treatment ammonia nitrogen waste water
WO2021079818A1 (en) * 2019-10-25 2021-04-29 パナソニックＩｐマネジメント株式会社 Water treatment device
CN112755967A (en) * 2020-12-15 2021-05-07 武汉大学 Chitin nano fiber porous composite microsphere blood ammonia adsorbent, preparation method and application thereof
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CN112759184A (en) * 2020-12-17 2021-05-07 十堰碧蓝环保科技有限公司 Little plastics clean-up piece-rate system in dangerous waste liquid
CN113016567A (en) * 2021-03-02 2021-06-25 黑龙江省农业科学院 Irrigation system for improving quality and increasing efficiency of rice
CN115779853A (en) * 2021-09-09 2023-03-14 中国科学院城市环境研究所 Preparation method and application of waste nitric acid adsorbent

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