CN108160047A - A kind of coal-fired flue-gas goes the preparation method of the modified zeolite of the load nano zero valence iron of lead - Google Patents
A kind of coal-fired flue-gas goes the preparation method of the modified zeolite of the load nano zero valence iron of lead Download PDFInfo
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- CN108160047A CN108160047A CN201810002357.1A CN201810002357A CN108160047A CN 108160047 A CN108160047 A CN 108160047A CN 201810002357 A CN201810002357 A CN 201810002357A CN 108160047 A CN108160047 A CN 108160047A
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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Abstract
The preparation method of the modified zeolite of the load nano zero valence iron of the load nano zero valence iron of lead is gone the invention discloses a kind of coal-fired flue-gas, is included the following steps：Pretreatment prepares Nanoscale Iron, the modified zeolite of synthesis load nano zero valence iron, dry washing.The high reproducibility of Zero-valent Iron is not only utilized in nano zero valence iron prepared by the present invention, herein in connection with and improve the chelating suction-operated of the high adsorption matter and chitosan of zeolite to lead, simple substance Pb and compound state PbCl in coal-fired flue-gas can be adsorbed2Form existing for Pb, to greatest extent remove coal-fired flue-gas in heavy metal pollution.
Description
Technical field
The present invention relates to purifying coal-fired flue gas fields, and in particular to the load nano zero-valence of lead is removed to a kind of coal-fired flue-gas
The preparation method of the modified zeolite of iron.
Background technology
Lead is a heavy metal species, is one of the metal that the mankind use earliest, can be used for build, lead-acid accumulator, bullet,
Shell, welding material, fishing tackle, fishery apparatus, radiation protection material, trophy, sulfuric acid corrosion resistant, anti-ionising radiation, accumulator
Deng material portions alloy, alloy can make font, bearing, cable sheathing etc. and be used, and can also make athletic sports appliance shot, etc.
Deng.Lead is a kind of toxic heavy metal done great harm to human body, thus lead and its compound enter after body will to nerve, make
Multiple systems such as blood, digestion, kidney, angiocarpy and endocrine damage, and lead poisoning can be caused if too high levels.Lead can not
It degrades again, once being discharged into environment, still maintains its toxicity for a long time.Due to the long-term persistence of lead in the environment, and to being permitted
More vital tissues have stronger potentiality toxicity, so lead is put into strong pollutant range always.
Coal fired power plant is one of primary discharge source of heavy metal pollution.It is looked forward to it is estimated that China produces at present from thermoelectricity every year
The lead gross mass of industry discharge is between 97.2-168.2t.Lead in coal is primarily present or is incorporated in sulfide, the lead in coal with
Sulphur has apparent positive correlation.Lead in coal volatilizees in combustion, with simple substance Pb and compound state PbCl2Etc. forms release,
Air is drained into the lead particle and gas phase of sub-micron.In CHINESE COAL the average value of lead be 13.0 μ g/g, different coal-forming areas
The content difference of Pb is larger in domain, according to the difference of Pb contents in coal, marks off low lead coal (Pb20 μ g/g), middle lead coal (Pb20 μ
G/g-40 μ g/g), high three different grade scales of lead coal (Pb40 μ g/g).《Atmosphere pollutants emission standards》(GB116297-
1996) it is provided in, lead and its compound concentration must not exceed 0.7mg/m3.The removal of lead has important environmental protection meaning in coal-fired flue-gas
Justice, is conducive to preserve the ecological environment and health.
Nano zero-valence iron particle has higher specific surface area and excellent adsorption and chemical reactivity, can be to ring
It halogenated torch in border, Polychlorinated biphenyls (PCB), organo-chlorine pesticide, insecticide, dyestuff, heavy metal ion, nitrate, inscription hydrochlorate and moans
The multiple pollutants such as hydrochlorate carry out reduction reparation；Zeolite has larger ratio as the natural minerals for being distributed wide, large storage capacity
Surface area and charging performance can have a variety of catalysis and absorption property after modification；Load technology is generally by high warm forging
Burning or ion exchange, by the nano zero valence iron particulate load to solid carrier of generation, this makes it possible to reduce to reunite, enhancing is received
The transfer abilities of meter Tie in the environment, are conducive to the reparation to soil, underground water and polluted river.Therefore, art technology
Personnel have carried out the environmentally friendly application study of the modified zeolite of load nano zero valence iron.
104722279 A of CN disclose a kind of alginic acid uranium/gelatin cladding nano zero valence iron go in water removal heavy metal every,
The method of land pollutant, and specifically disclose following preparation process：Na-alginate is molten in 50-65 DEG C of stirred in water bath with gelatin
It solves, after ultrasonic deaeration 10-20min, obtains alginic acid uranium/gelatin mixed solution；Under nitrogen protective condition, received freshly prepared
Rice Fe0Particle is mixed with alginic acid uranium/gelatin solution:After ultrasonic disperse 10-20min, nanometer Fe is obtained0With alginic acid uranium/gelatin
Blend:Blend is added to CaC1 dropwise with dropper or through peristaltic pump2In solution, cross-linking reaction under the conditions of magnetic agitation
30-60min obtains black SA/Gel cladding nano zero valence iron gel balls.However, this method load synergistic effect is not prominent enough,
It is difficult to obtain preferable adsorption effect.
105148885 A of CN disclose one kind for removing Br03And Cl04Nanometer iron hammer modified zeolite and its prepare and
Using, and specifically disclose following preparation method:Screening, acid-base pretreatment, Ran Hou are first crushed to natural clinoptilolite
In polyethylene glycol Lip river liquid at 120-140 DEG C, by zeolite and FeC13、MnS04It adds and stirs evenly by weight mixing, react
After 10-20min into mixed liquor plus NaOH solution to black suspension object is not further added by, by mixture after the reaction was continued 20-30min
Filtering, elution, solid can be prepared by after drying to constant weight described for removing Br03And C104Nanometer ferrimanganic modified zeolite.
However, this method can be only applied to sewage treatment field, it is impossible to the absorption applied to gas Pb simple substance.
To sum up, present technology still lacks a kind of modification for being capable of lead simple substance and lead compound present in adsorbed gas environment
Zeolite.
Invention content
The preparation of the modified zeolite of the load nano zero valence iron of lead is gone the object of the present invention is to provide a kind of coal-fired flue-gas
The high reproducibility of Zero-valent Iron is not only utilized in method, prepared modified zeolite, while improves the high adsorption matter of zeolite, with
And chelating suction-operated of the chitosan to lead, simple substance Pb and ion Pb in coal-fired flue-gas can be adsorbed2+, to remove combustion to greatest extent
Heavy metal contaminants in flue-gas.
The technical solution adopted by the present invention is as follows.
A kind of coal-fired flue-gas goes the preparation method of the modified zeolite of the load nano zero valence iron of lead, includes the following steps：
(1) it pre-processes：By zeolite 1-5mol/L HNO3Solution stirs 8-12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards for several times；Natural zeolite often containing other minerals impurity, passes through HNO3It cleans up；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in deionized water, adds in FeSO later4·
7H2O simultaneously uses HNO3Solution is transferred to pH as 2-5, reducing agent solution is then added in, and be stirred at room temperature 20-60 minutes, synthesizes
Load the zeolite of nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：Polymeric sorbent and table are added in into the solution of step (2)
Face activating agent, and under ultrasound condition and stirred 30-60 minutes at a temperature of 20-60 DEG C, obtain black spherical particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 12-24 hours, vacuum filtration is consolidated
Body product, then deionized water cleaning for several times, be dried in vacuo to get to load nano zero valence iron modified zeolite.
Preferably, FeSO in the step (2)4·7H2O is 1-3 with zeolite mass ratio:10.
Preferably, the speed of the stirring in the step (2) is 600-900r/min；The reducing agent solution is
The solution that NaBH4 is formulated with deionized water, reducing agent quality and the FeSO4·7H2The mass ratio of O is 3-6:10.
In the step (2), existing reaction equation is：Fe2++2BH4 -+6H2O→Fe0+2B(OH)3+7H2。
Preferably, polymeric sorbent is chitosan in the step (3), the quality that the chitosan adds in it is described
FeSO4·7H2The mass ratio of O is 0.01-0.1:1.
Preferably, in the step (3) surfactant be 4- nonyl phenol ethoxylates, the 4- nonyl phenols ethoxy
The quality of the addition of glycolylate and the FeSO4·7H2The mass ratio of O is 0.001-0.01:1.
Preferably, step (3) controlling reaction temperature is 40 DEG C.
In addition, the present invention also provides the modified zeolites of load nano zero valence iron prepared by above-mentioned preparation method.
In addition, lead is removed for coal-fired flue-gas invention further provides the modified zeolite.
Beneficial effects of the present invention：
(1) the technical program uses rational Nanoscale Iron support materials, and combines polymeric sorbent synergistic sorption ability,
Using surfactant-dispersed nano particle so that lead ion can not only be restored by loading the modified zeolite of nano zero valence iron, and
And its surface tension is increased, effectively adsorb elementary lead.
(2) the technical program so that reaction condition is controllable using rational proportioning and specific temperature, pH, realizes load
The optimization of the modified zeolite of nano zero valence iron.
Specific embodiment
The specific embodiment of the present invention is described further below：
Embodiment 1 prepares the modified zeolite A1 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：Added in into the solution of step (2) 10 grams of chitosans and
1 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and stirred 60 minutes at a temperature of 60 DEG C, obtain spherical of black
Grain；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A1.
Embodiment 2 prepares the modified zeolite A2 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：Added in into the solution of step (2) 2 grams of chitosans and
0.2 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and stirred 60 minutes at a temperature of 60 DEG C, obtain spherical of black
Grain；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A2.
Embodiment 3 prepares the modified zeolite A3 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：Added in into the solution of step (2) 1 gram of chitosan and
0.1 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and stirred 60 minutes at a temperature of 60 DEG C, obtain spherical of black
Grain；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A3.
Embodiment 4 prepares the modified zeolite A4 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：0.9 gram of chitosan is added in into the solution of step (2)
It with 0.09 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and is stirred 60 minutes at a temperature of 60 DEG C, obtains black ball
Shape particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A4.
Embodiment 5 prepares the modified zeolite A5 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：0.8 gram of chitosan is added in into the solution of step (2)
It with 0.08 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and is stirred 60 minutes at a temperature of 60 DEG C, obtains black ball
Shape particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A5.
Embodiment 6 prepares the modified zeolite A6 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：0.7 gram of chitosan is added in into the solution of step (2)
It with 0.07 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and is stirred 60 minutes at a temperature of 60 DEG C, obtains black ball
Shape particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A6.
Embodiment 7 prepares the modified zeolite A7 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：0.6 gram of chitosan is added in into the solution of step (2)
It with 0.06 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and is stirred 60 minutes at a temperature of 60 DEG C, obtains black ball
Shape particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A7.
Embodiment 8 prepares the modified zeolite A8 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：0.5 gram of chitosan is added in into the solution of step (2)
It with 0.05 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and is stirred 60 minutes at a temperature of 60 DEG C, obtains black ball
Shape particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A8.
Embodiment 9 prepares the modified zeolite A9 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：0.4 gram of chitosan is added in into the solution of step (2)
It with 0.04 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and is stirred 60 minutes at a temperature of 60 DEG C, obtains black ball
Shape particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A9.
Embodiment 10 prepares the modified zeolite A10 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：0.3 gram of chitosan is added in into the solution of step (2)
It with 0.03 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and is stirred 60 minutes at a temperature of 60 DEG C, obtains black ball
Shape particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A10.
Embodiment 11 prepares the modified zeolite A11 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：0.2 gram of chitosan is added in into the solution of step (2)
It with 0.02 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and is stirred 60 minutes at a temperature of 60 DEG C, obtains black ball
Shape particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A11.
Embodiment 12 prepares the modified zeolite A12 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：0.1 gram of chitosan is added in into the solution of step (2)
It with 0.01 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and is stirred 60 minutes at a temperature of 60 DEG C, obtains black ball
Shape particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A12.
Embodiment 13 prepares the modified zeolite A13 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：0.05 gram of chitosan is added in into the solution of step (2)
It with 0.005 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and is stirred 60 minutes at a temperature of 60 DEG C, obtains black ball
Shape particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A13.
Embodiment 14 prepares the modified zeolite A14 of load nano zero valence iron
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：0.01 gram of chitosan is added in into the solution of step (2)
It with 0.001 gram of 4- nonyl phenol ethoxylate, and under ultrasound condition and is stirred 60 minutes at a temperature of 60 DEG C, obtains black ball
Shape particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning three times, be dried in vacuo to get to load nano zero valence iron modified zeolite A13.
Comparative example 1 prepares the modified zeolite B1 of the load nano zero valence iron of not chitosan-containing
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：0.1 gram of 4- nonyl phenol second is added in into the solution of step (3)
Oxygroup compound, and under ultrasound condition and stirred 60 minutes at a temperature of 60 DEG C, obtain black spherical particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then deionized water cleaning for several times, vacuum drying, obtain product be not the load nano zero valence iron of chitosan-containing change
Property zeolite B1.
Comparative example 2 prepares the modified zeolite B2 of the load nano zero valence iron without 4- nonyl phenol ethoxylates
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：1 gram of chitosan is added in into the solution of step (3), and super
It under the conditions of sound and is stirred 60 minutes at a temperature of 60 DEG C, obtains black spherical particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 24 hours, vacuum filtration obtains solid
Product, then for several times, vacuum drying, it is that the load without 4- nonyl phenol ethoxylates is received to obtain product for deionized water cleaning
The modified zeolite B2 of rice Zero-valent Iron.
Comparative example 3 prepares the modified boiling of the load nano zero valence iron of not chitosan-containing and 4- nonyl phenol ethoxylates
Stone B3
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in 200 grams of deionized waters, is added in later
FeSO4·7H2O and with 1mol/L HNO3Solution is transferred to pH as 2-5, then adds in and contains 4 grams of NaBH4The 50ml reduction of configuration
Agent solution, and be stirred at room temperature 60 minutes, the zeolite of synthesis load nano zero valence iron；
(3) dry washing：Step (2) is stood 24 hours, vacuum filtration obtains solid product, and then deionized water is cleaned
For several times, be dried in vacuo, obtain product be not the load nano zero valence iron of chitosan-containing and 4- nonyl phenol ethoxylates change
Property zeolite B3.
Comparative example 4 prepares loading chitosan zeolite B4
(1) it pre-processes：By 50 grams of zeolite 1mol/L HNO3Solution stirs 12 hours, pickling to remove impurity, spend from
Sub- water washing is dried afterwards three times；
(2) 1 gram of chitosan is added in into the solution of step (2), and under ultrasound condition and stirs 60 at a temperature of 60 DEG C
Minute, obtain black spherical particle；
(3) dry washing：The black spherical particle obtained in step (2) is stood 24 hours, vacuum filtration obtains solid
Product, then for several times, vacuum drying obtains the zeolite B4 that product is loading chitosan for deionized water cleaning.
Application Example
Above-mentioned product is prepared into packing layer, then inserts the packing layer in coal-fired flue-gas adsorption tower, uses same a batch
Coal-fired flue-gas to be measured flows through packing layer, meanwhile, on packing layer spray pH be 4 slurries, help packing layer cooling and more
Good absorption.Then, by measuring the lead concentration of coal-fired flue-gas import and outlet, following result of the test is obtained, as shown in table 1.
Table 1
As can be seen from Table 1, the adsorption effect of A groups is better than the effect of B groups, and the effect of A3-A12 is far superior to B groups
Effect, illustrate the technical program prepare load nano zero valence iron modified zeolite, be loaded with chitosan and 4- nonyl phenol second
Oxygroup compound has preferable adsorption effect, chelating suction-operated of the chitosan to lead, and reproducibility high with nano zero valence iron generates
Synergistic effect, can preferably adsorb the lead in flue gas.
In addition, as can be seen from Table 1, the effect of A3-A12 is the adsorption effect of far superior to A1, A2, A13, A14 group, is said
It is bright easily to block the porous of zeolite when the too high levels of chitosan and 4- nonyl phenol ethoxylates, absorption is caused to imitate instead
Fruit declines, and when the concentration of chitosan and 4- nonyl phenol ethoxylates is too low, and the molecule not formed forms synergistic sorption and makees
With therefore, the quality proportioning of A3-A12 can just obtain synergistic sorption effect.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is changed.Therefore, the invention is not limited in specific embodiment disclosed and described above, to the one of invention
A little modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, it although is used in this specification
Some specific terms, but these terms are merely for convenience of description, do not limit the present invention in any way.
Claims (8)
1. a kind of coal-fired flue-gas goes the preparation method of the modified zeolite of the load nano zero valence iron of lead, which is characterized in that including
Following steps：
(1) it pre-processes：By zeolite 1-5mol/L HNO3Solution stirs 8-12 hours, and pickling uses deionized water to remove impurity
Washing is dried afterwards for several times；
(2) Nanoscale Iron is prepared：Zeolite pretreated in step (1) is added in deionized water, adds in FeSO later4·7H2O
And use HNO3Solution is transferred to pH as 2-5, then adds in reducing agent solution, and be stirred at room temperature 20-60 minutes, synthesis load
The zeolite of nano zero valence iron；
(3) modified zeolite of synthesis load nano zero valence iron：Polymeric sorbent is added in into the solution of step (2) and surface is lived
Property agent, and under ultrasound condition and stirred 30-60 minutes at a temperature of 20-60 DEG C, obtain black spherical particle；
(4) dry washing：The black spherical particle obtained in step (3) is stood 12-24 hours, vacuum filtration obtains solid production
Object, then deionized water cleaning for several times, be dried in vacuo to get to load nano zero valence iron modified zeolite.
A kind of 2. preparation method as described in claim 1, which is characterized in that FeSO in the step (2)4·7H2O and zeolite
Mass ratio is 1-3:10.
3. a kind of preparation method as claimed in claim 2, which is characterized in that the speed of the stirring in the step (2) is
600-900r/min；The reducing agent solution is NaBH4The solution being formulated with deionized water, reducing agent quality with it is described
FeSO4·7H2The mass ratio of O is 3-6:10.
4. a kind of preparation method as claimed in claim 2 or claim 3, which is characterized in that polymeric sorbent is in the step (3)
Chitosan, the quality that the chitosan adds in and the FeSO4·7H2The mass ratio of O is 0.01-0.1:1.
5. a kind of preparation method as claimed in claim 3, which is characterized in that surfactant is 4- nonyls in the step (3)
Base phenol ethoxylate, quality and the FeSO of the addition of the 4- nonyl phenol ethoxylates4·7H2The mass ratio of O is
0.001-0.01:1。
6. a kind of preparation method as claimed in claim 5, which is characterized in that the temperature in the step (3) is 40 DEG C.
7. the modified of load nano zero valence iron prepared by a kind of preparation method by claim 1-6 any one of them is boiled
Stone.
8. the purposes of the modified zeolite described in claim 7, which is characterized in that the modified zeolite removes lead for coal-fired flue-gas.
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Denomination of invention: A preparation method of modified zeolite loaded with nano zero valent iron for removing lead from coal-fired flue gas Effective date of registration: 20220523 Granted publication date: 20201225 Pledgee: Bank of China Limited Guangzhou Pearl River Branch Pledgor: GUANGDONG JIADE ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Registration number: Y2022440000098 |