CN107398257A - A kind of preparation method and application of modified zeolite molecular sieve adsorption particle - Google Patents
A kind of preparation method and application of modified zeolite molecular sieve adsorption particle Download PDFInfo
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- CN107398257A CN107398257A CN201710878345.0A CN201710878345A CN107398257A CN 107398257 A CN107398257 A CN 107398257A CN 201710878345 A CN201710878345 A CN 201710878345A CN 107398257 A CN107398257 A CN 107398257A
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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
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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
- B01J20/02—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
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Abstract
The invention belongs to water-treatment technology field, and in particular to a kind of preparation method and application of modified zeolite molecular sieve adsorption particle.Technical scheme is as follows：A kind of preparation method of modified zeolite molecular sieve adsorption particle, comprises the following steps：Chitosan acetic acid colloidal sol and acetic acid zinc solution are made into first, chitosan acetic acid colloidal sol is instilled in acetic acid zinc solution and carries out complex reaction at ambient temperature, and modification of chitosan zinc solution is made；Then zeolite molecular sieve is put into sodium alginate soln and be crosslinked, the zeolite molecular sieve after crosslinking is taken out and is put into modification of chitosan zinc solution, after concussion is dried, obtain modified zeolite molecular sieve adsorption particle.The preparation method and application of modified zeolite molecular sieve adsorption particle provided by the invention, form the adsorption particle that ammonia nitrogen function is removed with low temperature, the adsorption particle can be used as filtering media application to propose mark transformation in water factory, new structures need not be increased, do not produce accessory substance, can reach cryogenic conditions go down water removal in ammonia nitrogen target.
Description
Technical field
The invention belongs to water-treatment technology field, and in particular to a kind of preparation method of modified zeolite molecular sieve adsorption particle
And application.
Background technology
In northern China severe cold area, due to the influence of the factors such as climate, temperature, geographical position, winter source water is normal
It is low to there is water quality temperature, the problem of water treatment efficiency difference；And with industrial or agricultural technology and Development of Urbanization, ammonia and nitrogen pollution is increasingly
Seriously, winter raw water water temperature is relatively low in addition, and conventional water treatment process can not effectively remove ammonia nitrogen in water removal, cause effluent quality can not
Meet《Standards for drinking water quality》(GB5749-2006).
At present, for the processing method of ammonia nitrogen in water, existing water factory typically uses break point chlorination, but the meeting in processing procedure
The DBPs such as chloramines, chlorinatedorganic are produced, cause secondary pollution of water, while add the ill and carcinogenic of drinking person
Risk.Had at normal temperatures to ammonia nitrogen using biologic pretreatment method (bio-contact oxidation and biofilter) and preferably remove effect
Fruit, but change of the biological pre-treatment process to traditional handicraft is larger, it is necessary to newly-increased structures and floor space, initial investment cost
It is higher, and bioactivity is influenced by environmental temperature, limits practical application of the technique in northern frore area water factory.
4A zeolite molecular sieves are a kind of alumino-silicate compounds with cubic lattice, and specific surface area is big, can be diameter
For small Molecular Adsorption to inside vestibule, it is internal to have uniform microcellular structure, can be with the ion progress ion exchange in environment
Without changing crystal structure, 4A zeolite molecular sieves have because of its special ion-exchange capacity and absorption property in Water purification field
There is preferable application prospect.Chitosan (CTS) is a kind of natural flocculating agent, and it is widely present in shellfish, due to it
Contain substantial amounts of amino and hydroxyl isoreactivity group in molecular structure, property is more active, can modify, activates and be coupled, therefore can
To occur a variety of chemical modifications, and can couple to form multifunctional composite with sorbing material, coagulant, microorganism etc.,
There is quite wide application prospect in water process especially drinking water treatment field.
The content of the invention
The present invention provides a kind of preparation method and application of modified zeolite molecular sieve adsorption particle, and being formed, there is low temperature to remove ammonia
The adsorption particle of nitrogen function, the adsorption particle can be used as filtering media application to propose mark transformation in water factory, without increasing new structures, no
Produce accessory substance, can reach cryogenic conditions go down water removal in ammonia nitrogen target.
Technical scheme is as follows：
A kind of preparation method of modified zeolite molecular sieve adsorption particle, comprises the following steps：
(1) by acetum that the chitosan of deacetylation >=90% and concentration are 1%-5% according to 1:50-100 matter
Amount is configured to chitosan acetic acid colloidal sol than mixing；
(2) zinc acetate is dissolved in deionized water and acetic acid zinc solution is made, wherein the quality of zinc acetate and the chitosan
Than for 1:4；
(3) the chitosan acetic acid colloidal sol is instilled in the acetic acid zinc solution, stirs and evenly mixs, carry out at ambient temperature
Complex reaction, reaction time 10-18h, obtain modification of chitosan zinc solution；
(4) 50g zeolite molecular sieves are rinsed well with deionized water, being put into the complete 200-300ml concentration of dissolving is
5h is crosslinked in 1%-2% sodium alginate aqueous solutions；
(5) zeolite molecular sieve after crosslinking is taken out, is put into the modification of chitosan zinc solution, is subsequently placed in concussion
In device, oscillator 120~150r/min of rotating speed, 10h is shaken under room temperature condition, form zeolite molecular sieve and modification of chitosan zinc
Complex；
(6) zeolite molecular sieve and modification of chitosan Zn complex are taken out, are placed in vacuum drying chamber and dry 18h,
Temperature is 60 DEG C -70 DEG C, and modified zeolite molecular sieve adsorption particle is made.
The preparation method of described modified zeolite molecular sieve adsorption particle, wherein the zeolite molecular sieve aperture is 4A.
A kind of modified zeolite molecular sieve adsorption particle goes the application of ammonia nitrogen in water removal in low temperature, comprises the following steps：Utilize
Above-mentioned modified zeolite molecular sieve adsorption particle, the modified zeolite molecular sieve adsorption particle is put into containing ammonia nitrogen pollutant
It is stirred in water sample, the modified zeolite molecular sieve adsorption particle dosage is 3-5g/L, mixing time 4-5h, and stirring is fast
It is 4-35 DEG C to spend for 100-120r/min, range of reaction temperature, and ammonia nitrogen pollutant content is 4-6mg/L in water sample, and ammonia nitrogen is gone
Except rate reaches more than 90%.
A kind of modified zeolite molecular sieve adsorption particle goes another application of ammonia nitrogen in water removal, including following step in low temperature
Suddenly：Using above-mentioned modified zeolite molecular sieve adsorption particle, the modified zeolite molecular sieve adsorption particle is applied to adsorption column,
Adsorption column upper strata is modified zeolite adsorption particle, particle diameter 0.2-0.3cm, adsorption particle layer height 0.5m, and adsorption column lower floor is
Cobblestone supporting layer, it is highly 0.05m, filter tank average rate of filtering is 9-10m/h；Water sample containing ammonia nitrogen pollutant is entered by peristaltic pump
Enter modified zeolite molecular sieve adsorption column, filter off ammonia nitrogen in water removal, ammonia nitrogen pollutant content is 4-6mg/L in water sample, ammonia nitrogen
Clearance scope is 95%-99%.Wherein described adsorption column is provided with overfall and backwash water inlet, and backwashing period is
10-15d, temperature range are 4-35 DEG C.
Beneficial effects of the present invention are：
(1) modified zeolite molecular sieve adsorption particle prepared by the present invention is a kind of graininess water treatment agent, has and removes
The efficiency of ammonia nitrogen in micro-polluted water, because the oxygen atom in 4A zeolite molecular sieve skeletons is common to two neighboring tetrahedron, this
Kind structure can accommodate cation, and so as to carry out cation exchange reaction, therefore 4A zeolite molecular sieves have higher choosing to ammonia nitrogen
Choose friends transsexual.By the way that modification of chitosan and 4A zeolite molecular sieves are crosslinked, chitosan surface amino groups, hydroxyl isoreactivity are utilized
The chelatropic reaction that group occurs with metal ion, makes metal ion d orbital slots, is improved by the effect of coordinate bond to ammonia in water
The adsorption capacity of nitrogen small molecule, so as to strengthen removal efficiency of the 4A zeolite molecular sieves to ammonia nitrogen.
(2) cost of investment of the present invention is low, cold operation effect is good, the regeneration period is long, recoverable, constructs without newly-increased
Thing, transformed suitable for Large Water Works filtering technique section, and the application of small-scale integration apparatus.
Brief description of the drawings
Fig. 1 is the modified zeolite molecular sieve adsorption particle scanning electron microscopic picture prepared in embodiment 1；
Fig. 2 is the adsorption column installation drawing using modified zeolite molecular sieve adsorption particle as filtrate；
Wherein：1：Water tank；2：Peristaltic pump；3：Flowmeter；4：Water inlet；5：Modified zeolite molecular sieve adsorption particle filtrate；6：
Cobblestone supporting layer；7：Water outlet；8：Backwash water inlet；
Fig. 3 is modified zeolite molecular sieve curve of adsorption kinetics；
Fig. 4 is modified zeolite molecular sieve pseudo-first-order kinetic curve；
Fig. 5 is modified zeolite molecular sieve pseudo-second order kinetic curve；
Fig. 6 is modified zeolite molecular sieve adsorption isotherm model analysis；
Fig. 7 is the lnK of modified zeolite molecular sieve absorption ammonia nitrogendWith 1/T graphs of a relation.
Embodiment
Following specific embodiments are the further explanations to present invention, but the substantive content of the present invention is not limited in
Described in following specific embodiments, any combination between any specific embodiment and this hair is belonged to the simple change of preparation process
Bright required protection domain.
Embodiment 1
The preparation method of the modified zeolite molecular sieve adsorption particle of the present embodiment follows the steps below：
(1) by acetum that the chitosan of deacetylation 90% and concentration are 2% according to 1:50 mass ratio mixing, matches somebody with somebody
Chitosan acetic acid colloidal sol is made；
(2) zinc acetate is dissolved in deionized water and acetic acid zinc solution is made, wherein zinc acetate is molten with preparing chitosan acetic acid
The mass ratio of chitosan used is 1 during glue:4；
(3) chitosan acetic acid colloidal sol obtained by step (1) is instilled in acetic acid zinc solution, stirred and evenly mixed, at ambient temperature
Complex reaction is carried out, reaction time 10h, obtains modification of chitosan zinc solution；
(4) 50g zeolite molecular sieves are rinsed well with deionized water, it is 1% marine alga to be put into the complete 200ml concentration of dissolving
5h is crosslinked in acid sodium aqueous solution；
(5) zeolite molecular sieve after crosslinking is taken out and be put into modification of chitosan zinc solution obtained by step (3), then put
The rotating speed 120r/min in oscillator, 10h is shaken under room temperature condition, form the cooperation of zeolite molecular sieve and modification of chitosan zinc
Thing；
(6) gained zeolite molecular sieve in step (5) is taken out with modification of chitosan Zn complex, is placed in vacuum drying chamber
18h is dried in (60 DEG C), modified zeolite molecular sieve adsorption particle is made.
Wherein, described zeolite molecules mesh size is 4A.
Prepared modified zeolite molecular sieve adsorption particle is observed using ESEM, as shown in figure 1, particle table
Face is without sclay texture, and rough surface out-of-flatness, and more protruding features are presented.
The modified zeolite molecular sieve adsorption particle of the present embodiment removes the application of ammonia nitrogen in low temperature water, as shown in Fig. 2 according to
Following steps are carried out：
The modified zeolite molecular sieve adsorption particle of embodiment is applied to adsorption column, adsorption column upper strata is adsorbed for modified zeolite
Particle 5, particle diameter 0.2-0.3cm, adsorption particle layer height 0.5m, lower floor are cobblestone supporting layer 6, are highly 0.05m, filter tank
Average rate of filtering is 9.5m/h；Raw water containing ammonia nitrogen pollutant enters modified zeolite molecular sieve adsorption column by peristaltic pump 2, filters off
Ammonia nitrogen in water removal, the clearance scope of ammonia nitrogen is 95%-99%；Wherein, described adsorption column is provided with overfall and backwash
Water inlet 8, backwashing period 15d.
The described range of reaction temperature for removing ammonia nitrogen in water removal is 4-5 DEG C.
Ammonia nitrogen pollutant concentration range is 4-6mg/L in described raw water.
Embodiment 2
The preparation method of the modified zeolite molecular sieve adsorption particle of the present embodiment follows the steps below：
(1) by acetum that the chitosan of deacetylation 95% and concentration are 5% according to 1:100 mass ratio mixing,
It is configured to chitosan acetic acid colloidal sol；
(2) zinc acetate is dissolved in deionized water and acetic acid zinc solution is made, wherein zinc acetate is molten with preparing chitosan acetic acid
The mass ratio of chitosan used is 1 during glue:4；
(3) chitosan acetic acid colloidal sol obtained by step (1) is instilled in acetic acid zinc solution, stirred and evenly mixed, at ambient temperature
Complex reaction is carried out, reaction time 18h, obtains modification of chitosan zinc solution；
(4) 50g zeolite molecular sieves are rinsed well with deionized water, it is 2% marine alga to be put into the complete 300ml concentration of dissolving
5h is crosslinked in acid sodium aqueous solution；
(5) zeolite molecular sieve after crosslinking is taken out and be put into modification of chitosan zinc solution obtained by step (3), then put
The rotating speed 150r/min in oscillator, 10h is shaken under room temperature condition, form the cooperation of zeolite molecular sieve and modification of chitosan zinc
Thing；
(6) gained zeolite molecular sieve in step (5) is taken out with modification of chitosan Zn complex, is placed in vacuum drying chamber
18h is dried in (70 DEG C), modified zeolite molecular sieve adsorption particle is made.
Wherein, described zeolite molecules mesh size is 4A.
The adsorption dynamics adsorption kinetics research of the modified zeolite molecular sieve adsorption particle of the present embodiment, as shown in Fig. 3, Fig. 4, Fig. 5, is pressed
Carried out according to following steps：
By modified zeolite molecular sieve adsorption particle 1.0g be placed in 100mL mass concentrations scope for 4~5mg/L ammonia nitrogen solutions in
In ground conical flask, conical flask is placed in gas bath constant temperature oscillator, (10 DEG C) vibrations under 200r/min, cryogenic conditions, respectively
Sample is taken out in 15,30,60,120,180,240,300,360,420,480,540,600,660 and 720min, filtered
0.45um miillpore filters, ammonia nitrogen concentration is determined using Nessler's reagent photometer.
The curve of adsorption kinetics of modified zeolite molecular sieve adsorption particle is modified as shown in figure 3, before starting the reaction in 1h
The rate of adsorption of zeolite molecular sieve adsorption particle is fast, and linear absorption, adsorbance reaches 0.214mg/g, with the reaction time
Carry out, the rate of adsorption is gradually slack-off, and adsorbance slowly rises；When reaction proceeds to 12h, adsorption equilibrium, modified zeolite are reached
The equilibrium adsorption capacity 0.286mg/g of molecular sieve adsorption particle.
In order to accurately react the ammonia nitrogen concentration trend that (10 DEG C) change over time under cryogenic and disclose its suction
Attached process, modified zeolite molecular sieve adsorption particle is carried out using Lagergren pseudo-first-orders and quasi- second- order reaction kinetics model
The fitting of test data,
Lagergren pseudo-first-order kinetics equations：
Lagergren pseudo-second order kinetic equations：
By modified zeolite molecular sieve adsorption particle (10 DEG C) adsorption dynamics adsorption kinetics data under cryogenic, to 1/qtWith 1/t
Relation and t/qtLinear fit (as shown in Figure 4 and Figure 5) is carried out with t relation, can be distinguished by the slope and intercept of straight line
Try to achieve parameter qe1、k1、qe2、k2, the results are shown in Table 1.
The kinetic parameter of table 1
Pass through the linearly dependent coefficient R to fitting2It is compared and understands, the linearly dependent coefficient of pseudo-second order kinetic fitting
(R2=0.999) it is higher than pseudo-first-order dynamics (R2=0.979), it can thus be concluded that, the process of modified zeolite molecular sieve absorption ammonia nitrogen is more
Meet pseudo-second order kinetic model.The equilibrium adsorption capacity being calculated by pseudo-first-order kinetics equation is respectively 0.317mg/g,
With result of the test obtained by modified zeolite molecular sieve adsorption particle (10 DEG C) under cryogenic equilibrium adsorption capacity 0.286mg/g phases
Difference is larger, and the data (0.299mg/g) and test value the data obtained of pseudo-second order kinetic equation model are very close.
Embodiment 3
The preparation method of the modified zeolite molecular sieve adsorption particle of the present embodiment follows the steps below：
(1) by acetum that the chitosan of deacetylation 90% and concentration are 3% according to 1:100 mass ratio mixing,
It is configured to chitosan acetic acid colloidal sol；
(2) zinc acetate is dissolved in deionized water and acetic acid zinc solution is made, wherein zinc acetate is molten with preparing chitosan acetic acid
The mass ratio of chitosan used is 1 during glue:4；
(3) chitosan acetic acid colloidal sol obtained by step (1) is instilled in acetic acid zinc solution, stirred and evenly mixed, at ambient temperature
Complex reaction is carried out, reaction time 18h, obtains modification of chitosan zinc solution；
(4) 50g zeolite molecular sieves are rinsed well with deionized water, it is 1% marine alga to be put into the complete 300ml concentration of dissolving
5h is crosslinked in acid sodium aqueous solution；
(5) zeolite molecular sieve after crosslinking is taken out and be put into modification of chitosan zinc solution obtained by step (3), then put
The rotating speed 150r/min in oscillator, 10h is shaken under room temperature condition, form the cooperation of zeolite molecular sieve and modification of chitosan zinc
Thing；
(6) gained zeolite molecular sieve in step (5) is taken out with modification of chitosan Zn complex, is placed in vacuum drying chamber
18h is dried in (70 DEG C), modified zeolite molecular sieve adsorption particle is made.
Wherein, described zeolite molecules mesh size is 4A.
The adsorption isotherm research of the modified zeolite of the present embodiment, as shown in fig. 6, following the steps below：
By modified zeolite molecular sieve adsorption particle 1.0g be placed in 100mL mass concentrations for 2,4,6,8,10,12mg/L ammonia nitrogens
Solution is placed in gas bath constant temperature oscillator in ground conical flask, by conical flask, (10 DEG C) vibrations under 200r/min, cryogenic conditions
After 12h adsorption equilibriums, 0.45um miillpore filters, measure filtrate ammonia nitrogen concentration C are filteredeCalculate modified zeolite molecular sieve equilibrium adsorption
Amount.
According to modified zeolite molecular sieve adsorption particle under cryogenic (10 DEG C), the vibration adsorption test number to ammonia nitrogen
According to, Langmuir and Freundlich isotherm adsorption models are respectively adopted and are fitted (Fig. 6), obtained respectively by Fig. 6 needed for
Parameter qm、KL、KFWith 1/n numerical value, 2 are the results are shown in Table.
Langmuir isothermal adsorpting equation formulas：
Freundlich isothermal adsorpting equation formulas：
The thermoisopleth parameter of table 2
From Fig. 6 and table 2, the absorption of (10 DEG C) to ammonia nitrogen etc. under cryogenic of modified zeolite molecular sieve adsorption particle
The result of warm line fitting shows, the multiple correlation coefficient (R of Langmuir adsorption isotherm line models2=0.999) it is higher than
Multiple correlation coefficient (the R of Freundlich adsorption isotherm line models2=0.989) Langmuir adsorption isotherm line model energy, is illustrated
More accurately description modified zeolite molecular sieve adsorbs the characteristic of ammonia nitrogen.1/n is different in Freundlich adsorption isotherm equations
Matter coefficient, generally, when 1/n is more than 2, illustrate that absorption is more difficult；When 1/n is equal to 1, linear adsorption is represented；1/n is more than 0.1
During less than 0.5, easily absorption is represented.The heterogeneous coefficient (1/n=0.499) of modified zeolite molecular sieve in this research, illustrate to be modified
The process of zeolite molecular sieve absorption ammonia nitrogen is easily carried out.According to Langmuir adsorption isotherm equations, the modified boiling being calculated
(10 DEG C) are 0.817mg/g to the monolayer maximal absorptive capacity of ammonia nitrogen in raw water under stone molecular sieve adsorption particle cryogenic conditions.
Embodiment 4
The preparation method of the modified zeolite molecular sieve adsorption particle of the present embodiment follows the steps below：
(1) by acetum that the chitosan of deacetylation 95% and concentration are 1% according to 1:70 mass ratio mixing, matches somebody with somebody
Chitosan acetic acid colloidal sol is made；
(2) zinc acetate is dissolved in deionized water and acetic acid zinc solution is made, wherein zinc acetate is molten with preparing chitosan acetic acid
The mass ratio of chitosan used is 1 during glue:4；
(3) chitosan acetic acid colloidal sol obtained by step (1) is instilled in acetic acid zinc solution, stirred and evenly mixed, at ambient temperature
Complex reaction is carried out, reaction time 15h, obtains modification of chitosan zinc solution；
(4) 50g zeolite molecular sieves are rinsed well with deionized water, it is 2% marine alga to be put into the complete 200ml concentration of dissolving
5h is crosslinked in acid sodium aqueous solution；
(5) zeolite molecular sieve after crosslinking is taken out and be put into modification of chitosan zinc solution obtained by step (3), then put
The rotating speed 120r/min in oscillator, 10h is shaken under room temperature condition, form the cooperation of zeolite molecular sieve and modification of chitosan zinc
Thing；
(6) gained zeolite molecular sieve in step (5) is taken out with modification of chitosan Zn complex, is placed in vacuum drying chamber
18h is dried in (70 DEG C), modified zeolite molecular sieve adsorption particle is made.
Wherein, described zeolite molecules mesh size is 4A.
The Adsorption thermodynamics research of the modified zeolite of the present embodiment, as shown in fig. 7, following the steps below：
Modified zeolite molecular sieve 1.0g is placed in 100mL mass concentrations scope in 4~5mg/L ammonia nitrogen solutions, to incite somebody to action respectively
Conical flask is placed in gas bath constant temperature oscillator, and respectively in 200r/min, temperature is shaken under the conditions of being 5 DEG C, 10 DEG C, 15 DEG C, 25 DEG C, 35 DEG C
After swinging 12h adsorption equilibriums, 0.45um miillpore filters are filtered, determine filtrate ammonia nitrogen concentration.
To calculate the thermodynamic parameter that modified zeolite molecular sieve adsorbs ammonia nitrogen, under experiment investigation different temperatures (5 DEG C, 10
DEG C, 15 DEG C, 25 DEG C, 35 DEG C) adsorption equilibrium state.Gibbs free (Δ G), enthalpy (Δ H), entropy (Δ S) pass through below equation
Calculate：
Δ G=-RTlnKd (7)
According to modified zeolite molecular sieve ammonia nitrogen during (5 DEG C, 10 DEG C, 15 DEG C, 25 DEG C, 35 DEG C) are to water under condition of different temperatures
Desorption balance data, the K under condition of different temperatures is calculated by formula (6)d, then corresponding temperature calculated by formula (7)
Jeep this free energy Δ G under the conditions of degree, finally by formula (8) to lnKdLinear fit is carried out (such as Fig. 7 institutes with 1/T relations
Show), enthalpy change (Δ H) corresponding to adsorption reaction and Entropy Changes (Δ S) can be calculated respectively by the slope and intercept of straight line, the results are shown in Table
3。
The adsorption thermodynamic parameters of table 3
From Fig. 7 and table 3, the enthalpy change Δ H of modified zeolite molecular sieve absorption ammonia nitrogen is on the occasion of illustrating modified zeolite molecule
The absorption sieved to ammonia nitrogen is the endothermic reaction, while the ability for illustrating to adsorb ammonia nitrogen increases with the rise of temperature.Temperature
Rise is advantageous to adsorption reaction progress, this free energy of (5 DEG C, 10 DEG C, 15 DEG C, 25 DEG C, 35 DEG C) jeep under condition of different temperatures
Become Δ G<0 is negative value, and with the rise of temperature, Δ G is less and less, and it is spontaneous process to show the adsorption process, simultaneously
Spontaneous degree is increasing with the rise of temperature.Entropy Changes Δ S>0 is on the occasion of showing absorption of the modified zeolite molecular sieve to ammonia nitrogen
Increase for entropy and react, and illustrate that avtive spot, the free degree of adsorbate and confusion degree all increase with the rise of temperature.
Claims (5)
1. a kind of preparation method of modified zeolite molecular sieve adsorption particle, it is characterised in that comprise the following steps：
(1) by acetum that the chitosan of deacetylation >=90% and concentration are 1%-5% according to 1:50-100 mass ratio
Mixing, is configured to chitosan acetic acid colloidal sol；
(2) zinc acetate is dissolved in deionized water and acetic acid zinc solution is made, the mass ratio of wherein zinc acetate and the chitosan is
1:4；
(3) the chitosan acetic acid colloidal sol is instilled in the acetic acid zinc solution, stirs and evenly mixs, be complexed at ambient temperature
Reaction, reaction time 10-18h, obtains modification of chitosan zinc solution；
(4) 50g zeolite molecular sieves are rinsed well with deionized water, it is 1%-2% to be put into the complete 200-300ml concentration of dissolving
5h is crosslinked in sodium alginate aqueous solution；
(5) zeolite molecular sieve after crosslinking is taken out, is put into the modification of chitosan zinc solution, is subsequently placed in oscillator
In, oscillator 120~150r/min of rotating speed, 10h is shaken under room temperature condition, form matching somebody with somebody for zeolite molecular sieve and modification of chitosan zinc
Compound；
(6) zeolite molecular sieve and modification of chitosan Zn complex are taken out, is placed in vacuum drying chamber and dries 18h, temperature
For 60 DEG C -70 DEG C, modified zeolite molecular sieve adsorption particle is made.
2. the preparation method of modified zeolite molecular sieve adsorption particle according to claim 1, it is characterised in that the zeolite
Molecular sieve bore diameter is 4A.
3. a kind of modified zeolite molecular sieve adsorption particle goes the application of ammonia nitrogen in water removal in low temperature, it is characterised in that including as follows
Step：Using modified zeolite molecular sieve adsorption particle as claimed in claim 1 or 2, the modified zeolite molecular sieve is adsorbed
Particle is put into the water sample containing ammonia nitrogen pollutant and is stirred, and the modified zeolite molecular sieve adsorption particle dosage is 3-
5g/L, mixing time 4-5h, mixing speed 100-120r/min, range of reaction temperature are 4-35 DEG C, and ammonia nitrogen is dirty in water sample
It is 4-6mg/L to contaminate thing content, and the clearance of ammonia nitrogen reaches more than 90%.
4. a kind of modified zeolite molecular sieve adsorption particle goes the application of ammonia nitrogen in water removal in low temperature, it is characterised in that including as follows
Step：Using modified zeolite molecular sieve adsorption particle as claimed in claim 1 or 2, the modified zeolite molecular sieve is adsorbed
Particle is applied to adsorption column, and adsorption column upper strata is modified zeolite adsorption particle, particle diameter 0.2-0.3cm, adsorption particle layer height
0.5m, adsorption column lower floor are cobblestone supporting layer, are highly 0.05m, and filter tank average rate of filtering is 9-10m/h；Containing ammonia nitrogen pollutant
Water sample modified zeolite molecular sieve adsorption column is entered by peristaltic pump, filter off ammonia nitrogen in water removal, ammonia nitrogen pollutant contains in water sample
Measure as 4-6mg/L, the clearance scope of ammonia nitrogen is 95%-99%.
5. modified zeolite molecular sieve adsorption particle according to claim 4 goes the application of ammonia nitrogen in water removal in low temperature, it is special
Sign is that the adsorption column is provided with overfall and backwash water inlet, backwashing period 10-15d, temperature range 4-35
℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710878345.0A CN107398257A (en) | 2017-09-26 | 2017-09-26 | A kind of preparation method and application of modified zeolite molecular sieve adsorption particle |
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| CN112707475A (en) * | 2019-10-25 | 2021-04-27 | 宁波方太厨具有限公司 | Adsorption powder, conductive polar plate, filter membrane and roll type filter element |
| CN113976074A (en) * | 2021-11-23 | 2022-01-28 | 沈阳建筑大学 | Iron-manganese mud composite gel ball adsorption antimony removal material and preparation method thereof |
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| CN113976074A (en) * | 2021-11-23 | 2022-01-28 | 沈阳建筑大学 | Iron-manganese mud composite gel ball adsorption antimony removal material and preparation method thereof |
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