CN108855010A - A kind of application of Uio-66/ poly aromatic composite material - Google Patents
A kind of application of Uio-66/ poly aromatic composite material Download PDFInfo
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- CN108855010A CN108855010A CN201810762580.6A CN201810762580A CN108855010A CN 108855010 A CN108855010 A CN 108855010A CN 201810762580 A CN201810762580 A CN 201810762580A CN 108855010 A CN108855010 A CN 108855010A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a kind of application of Uio-66/ poly aromatic amine composite material in the processing waste water of Cr containing sexavalence.The adsorbent that the present invention uses is that in aqueous solution, fragrant amine monomers pass through in situ chemical oxidative polymerization method, the Uio-66/ poly aromatic amine composite material of preparation in the surface Uio-66, its synthesis technology is simple, at low cost, high income, it is good to Cr in water (VI) removal effect, it is without secondary pollution.Under room temperature, the adsorbent maximal absorptive capacity is up to 263.69mg/g, and removal rate is up to 99% or more, higher than the chromium adsorbent material without compound Uio-66 and most of reports.It is handled using the method for the present invention and contains Cr (VI) acid waste water, have the characteristics that technical process is simple and convenient to operate, is good in economic efficiency.
Description
Technical field
The invention belongs to field of environment engineering technology, it is related to a kind of Uio-66/ poly aromatic amine composite material adsorbent and is locating
Manage the application method in sexavalence Cr waste water.
Background technique
The industries such as plating, process hides, metallurgy and Chemical Manufacture contain chromic acid per a large amount of chromate waste waters are discharged every year to environment
In waste water, chromium (VI) is mainly with Cr2O7 2‐And CrO4 2‐Form exist.Very harmful, the carcinogenic, teratogenesis, mutagenesis of chromium (VI),
The sustainable development of human health, the ecological balance and economic society is seriously endangered, pollution of chromium has caused worldwide wide
General concern.Therefore, China《Integrated wastewater discharge standard》(GB8978-1996) regulation in：The highest of chromium (VI) and total chromium permits
Perhaps concentration of emission is respectively 0.5 and 1.5mg/L.
Method of the conventional process containing chromium (VI) waste water has：Chemical precipitation method, electrolysis method, bioanalysis and absorption method etc..Change
Learning the precipitation method is most widely used chromium minimizing technology, it is advantageous that it is low in cost, it is easy to implement the method；Its drawback is to need a large amount of
Medicament is precipitated, and a large amount of chromed leather wastes can be generated, processing is difficult, returns molten risk, easily leads to secondary pollution.Electrolysis method processing
Chromate waste water effect stability, operation is relatively easy, but its shortcoming is that power consumption is consumed energy, steel and running expense are higher.Bioanalysis
Processing waste water is at low cost, and strain is selectively extensive, is not required to add a large amount of chemical reagent, environmental protection is without secondary pollution, but there is biology
The defects of cultivation cycle is long, not good enough to the treatment effect of extreme nature water body.
To avoid defect brought by conventional method, absorption method is a kind of feasible selection.Absorption method mainly utilizes absorption
Effective group selection absorption heavy metal ion in agent, it is easy to operate, it is high-efficient.The chromium that removes studied and used both at home and abroad at present is inhaled
Attached dose can be divided mainly into two class of inorganic adsorbent and organic adsorbent.The compounds such as iron, manganese, magnesium, aluminium are the most common inorganic suctions
Attached dose, and organic adsorbent includes natural and synthesising macromolecule copolymer, such as chitosan, alginic acid, cyclodextrin.But these are inhaled
Attached dose, there are still larger deficiency, is mainly shown as that adsorbent preparation process is complicated, at high cost, and absorption property is not good enough etc., such as fine coal
Ash, active carbon etc. are no more than 50mg/g etc. to the adsorbance of Cr (VI), significantly limit the absorbing process of processing waste water containing chrome
Using.Therefore, new adsorbent how is further developed, adsorbance, removal rate are improved, operating cost is reduced, for being electroplated, making
The advanced treating of industries acid waste water containing chromium such as leather and chromic salts is of great significance.
Uio-66 is a kind of metal-organic zirconium-based framework (MOFs), has high heat resistance, acid-alkali-corrosive-resisting, can be in water
It is stabilized in phase, is one of the series material in MOFs material with optimal stability.It has high-specific surface area, makes at present
The Uio-66 specific surface area synthesized with various methods is mostly more than 1000m2/ g has a good application prospect in many fields.
But Uio-66 surface functional group content is few, limits it in the application of adsorbing domain.By Uio-66 and gathering rich in functional group
It is the effective means being modified to its surface that it is compound, which to close object,.
Poly aromatic amine is a kind of conjugated polymer, has good environmental stability and redox characteristic, and surface contains
A large amount of amino, the application in fields such as water process have obtained extensive concern.But the poly aromatic amine specific surface area of synthesis is very low, and only ten
It is several to tens m2/ g significantly limits its application.
Therefore, a kind of composite material that can integrate both Uio-66 and poly aromatic amine advantage is developed, as waste water
Handling adsorbent is significantly.
Summary of the invention
It is acid in processing Cr containing sexavalence the purpose of the present invention is developing a kind of Uio-66/ poly aromatic amine composite material adsorbent
Application method on waste water, the adsorbent synthesis technology is simple, and high income is at low cost, and chromium ion adsorption capacity is big；For the first time by it
It is applied in processing field containing hexavalent chromium wastewater, provides a kind of easy to operate, user containing Cr (VI) acid waste water for processing
Just, effective method.The applicable processing in the industries such as plating, process hides and chromic salts acid waste water containing chromium.
The purpose of the present invention is what is be accomplished by the following way.
A kind of application of Uio-66/ poly aromatic amine composite material in the processing waste water of Cr containing sexavalence, the Uio-66/ are poly-
For aromatic amine composite material using Uio-66 as core, poly aromatic amine is shell.
The particle size range of above-mentioned composite material is between 200-800nm, and shell thickness is in 20-80nm or so.
Within the scope of above-mentioned partial size and shell thickness, increase with shell thickness, the specific surface area decline of composite material, although
Composite material overall adsorption performance boost, but the utilization rate of PmPD declines.
The application, further, by the acidity of Uio-66/ poly aromatic amine composite material processing Cr containing sexavalence
Waste water.
The application, the initial concentration of sexavalence Cr is 10-300mg/L, pH value 1-5 in the acid waste water.It is excellent
Selecting pH value is 2.
The application, further, it is 0.02g/L- that the Uio-66/ poly aromatic amine composite material, which is pressed solid-to-liquid ratio,
2g/L is added to the waste water mixing of the Cr containing sexavalence, and then oscillating reactions is separated by filtration.
The Uio-66/ poly aromatic amine composite material is further added to the useless of the Cr containing sexavalence by the application
Water mixing, then oscillating reactions 5-720min, is separated by filtration.
The preparation method of the Uio-66/ poly aromatic amine composite material includes the following steps, Uio- is added in the solution
66, and fragrant amine monomers, it stirs and evenly mixs；Then persulfate aqueous solution, initiated oxidation polymerization reaction is added dropwise, and continues to stir
Reaction is separated by solid-liquid separation, washs up to Uio-66/ poly aromatic amine composite material.
The mass ratio of Uio-66 described in above-mentioned preparation method and fragrant amine monomers is 1:5~1:0.25；It is preferred that 1：1‐
0.25；Further preferred 1:0.5.
In above-mentioned preparation method reaction system, the mass concentration of Uio-66 is 1~10g/L, preferably 4g/L, fragrant amine monomers
Mass concentration be 1~10g/L, preferably 2g/L.
Surfactant is added in above-mentioned preparation method reaction system, the surfactant includes detergent alkylate sulphur
The one or two of sour sodium, lauryl sodium sulfate.It is preferred that neopelex.
The mass ratio of Uio-66 described in above-mentioned preparation method and surfactant is 1:2~1:0.3, preferably 1:0.5.
The dosage of surfactant is excessive, and reaction system can generate many foams, and sample clean process can be very many and diverse and not
Easy cleaning is clean, and dosage is very few, spatial induction declines, i.e. the dispersibility of product is deteriorated.
Persulfate described in above-mentioned preparation method include one of sodium peroxydisulfate, ammonium persulfate, potassium peroxydisulfate or
It is several.
The molar ratio of persulfate described in above-mentioned preparation method and fragrant amine monomers is 1:1~3:1, preferably 1:1, mistake
The concentration of sulfate liquor is 0.01~0.5mol/L, preferably 0.025mol/L.
Above-mentioned preparation method first disperses Uio-66 in the aqueous solution containing surfactant, and aromatic amine is then added
Monomer stirs at least 0.5h, comes into full contact with it；Then it is water-soluble that persulfate is at the uniform velocity added with the rate of 0.5-10ml/min
Liquid, initiated oxidation polymerization reaction, and continue stirring until few 3h；It is separated by solid-liquid separation, washs up to Uio-66/ poly aromatic amine composite wood
Material.
It disperses Uio-66 in the aqueous solution containing surfactant in above-mentioned preparation method, after fragrant amine monomers are added
A whipping process is needed, it is come into full contact with.Mixing time at least 0.5h, preferably 0.5-24h, further preferred 0.5-2h.
Because having the process of a self assembly after monomer is added, being the effect by surfactant, fragrant amine monomers self assembly is made to exist
The surface of Uio-66, in this way after oxidant is added, fragrant amine monomers could polymerize in Uio-66 surface oxidation, after being formed
Core-shell structure, therefore they need a period of time to come into full contact with it, complete self assembly.
Persulfate solution cannot be rapidly joined in above-mentioned preparation method, slowly can only be at the uniform velocity added, preferably with 2.5ml/
Persulfate aqueous solution is added in the rate of min or so.
Initiated oxidation polymerization reaction in above-mentioned preparation method, and few 3h, preferably 3-24h are continued stirring until, further preferably
6h.Stirring is that the time is too short to be polymerize not exclusively in order to allow polymerization reaction sufficiently to carry out.
In the above method after the completion of oxidative polymerization, preferably reaction is carried out at 0~60 DEG C.It is preferred that centrifugation solid-liquid
Separation.
Beneficial effects of the present invention：
1) what the present invention was applied to wastewater treatment is a kind of new structural Uio-66/ poly aromatic amine composite material, the material
For material using Uio-66 as core, poly aromatic amine is shell.Composite material specific surface area reaches 319.77m2/ g effectively improves poly aromatic amine
Specific surface area, and amination modification successfully is carried out to the surface Uio-66, combine the advantage of two kinds of components.
2) the Uio-66/ poly aromatic amine composite material preparation process that the present invention is applied to wastewater treatment is simple and efficient.Because
The raw material Uio-66 nano particle scale of use is too small, easy to reunite in the solution, reduces the contact with poly aromatic amine molecule,
It is modified to be difficult to realize effective poly- surface.The present invention promotes Uio-66 particle interface hydrophobization, mentions by introducing surfactant
High particle dispersibility, to greatly improve the oxidation polymerization efficiency of poly aromatic amine, being prepared a kind of has core-shell structure
Uio-66/ poly aromatic amine composite material.It is also a kind of to be modified in Uio-66 nanostructured surface amination using aromatic amine
Method is the MOFs structural material pattern and surface modification of Uio-66 class, provides new thinking.
3) Uio-66 of the invention is synthesized using microwave method, and reaction is fast, high income；The fragrance amine monomers such as m-phenylene diamine (MPD) are dyes
The conventional raw material of the industrial circles such as material, coating, Uio-66 and aromatic amine recombination reaction carry out at normal temperature, the reaction item of no harshness
Part and special post-processing means are not required to, it is at low cost.Compared with without compound Uio-66, Uio-66/ poly aromatic amine composite wood
Material greatly improves product to the absorption property of Cr (VI).
4) the advantages of present invention gained composite material combines two kinds of components of Uio-66 and poly aromatic amine, and in aqueous solution
There is good stability, is conducive to the application in the fields such as water process.
5) Uio-66/ poly aromatic amine composite material adsorbent is applied to the spent acidic that processing contains Cr (VI) by the present invention for the first time
Water field；Can efficient process contain Cr (VI) acid waste water, adsorption capacity can reach 263.69mg/g, higher than the big portion reported at present
Divide adsorbent, and there is the features such as removal rate is high, easy to operate at low cost.
Detailed description of the invention：
Fig. 1 is that the SEM of 1 products therefrom of Examples 1 to 5 and comparative example schemes；
(a)Uio‐66/PmPD‐1:3(b)Uio‐66/PmPD‐1:1(c)Uio‐66/PmPD‐1:0.5；
(d)Uio‐66/PANI‐1:0.5(e)Uio‐66/PPY‐1:0.5(f)Uio‐66/PmPD‐1:0.5‐NSDS；
By (a), (b), (c) comparison it is found that the pattern of compound obtained by different composite ratio has differences, added with mPD
Amount increases, and compound is reunited, and comparison surface area generates certain influence, when dosage is reduced to 1：When 0.5, compound shape
Looks are uniform and disperse, as table 1 is listed；By (c), (d), (e) comparison it is found that different poly aromatic amine and the compound gained of Uio-66 are compound
The varying topography of object is little；By (c), (f) comparison it is found that surfactant is added, using the method for the hydrophobic oxidation polymerization in interface
The Uio-66/ poly aromatic amine compound dispersibility of synthesis is more preferable, it is compound more evenly.
Fig. 2 is 1 products therefrom of embodiment and the TEM figure and linear sweep graph for comparing Uio-66；
(a) the TEM figure of TEM figure (b) Uio-66/PmPD of Uio-66, as seen from the figure compared with Uio-66, the present invention is compound
The surface of material is more coarse, has wrapped up thin film, shows core-shell structure；
(c) across compound Uio-66@PmPD (1:0.5) diameter has carried out EDS line and has swept characterization (d), it can be seen that Zr
The part of core is mainly distributed on O element, C and N are more evenly distributed in entire scope, further demonstrate in compound
The composition of core-shell structure, i.e. Uio-66 have uniformly wrapped up one layer of PmPD.
Fig. 3 is 1 products therefrom of embodiment and compares the XRD spectrum of Uio-66 and compare the infared spectrum of PmPD；It (a) is real
It applies 1 products therefrom of example and compares the XRD diagram of Uio-66；(b) for 1 products therefrom of embodiment and compare Uio-66, PmPD it is infrared
Figure；
By XRD spectrum it is found that after compound the object phase composition of Uio-66 do not change, structure is not collapsed；
By infared spectrum it is found that in 3400-3000cm‐1Two absorption peaks are amino stretching vibration, in 1620cm‐1Near
Absorption correspond to quinoid structure, 746cm‐1Absorption peak corresponds to Zr-O key, and the characteristic absorption of two kinds of components is existed simultaneously in compound
Peak, and contain a large amount of amino.
To sum up, a series of characterization through patterns, structure and object phase can prove to be successfully prepared one kind using Uio-66 as core,
Poly aromatic amine is the composite material of shell.
Fig. 4 is the N of 1 products therefrom of embodiment2Adsorption and desorption isotherms；
As seen from the figure, which belongs to I class adsorption isotherm, shows to contain a large amount of micropores in composite material,
Speculate that these micropores are contributed by Uio-66.And the presence of a large amount of micropores is that compound has the important of high specific surface area
Reason.
Fig. 5 is embodiment 1-3 products therefrom and the thermal multigraph for comparing Uio-66, PmPD；
By analyzing thermal multigraph, and calculate according to the mass ratio of the residue of equation 1 load capacity of PmPD in compound.
Calculated result shows Uio-66 PmPD (1:0.5), Uio-66@PmPD (1:1), Uio-66@PmPD (1:3) corresponding composite wood
PmPD load capacity is respectively 11.50%, 25.83% and 56.30% (data are listed in table 1) in material.Obviously, reaction raw materials mPD is thrown
Enter than increasing, the ratio of PmPD in composite material can be obviously increased.It is calculated according to equation 2, if from compound adsorbance
The adsorbance for subtracting Uio-66, reuses the quality of PmPD in compound to calculate adsorption capacity, then Uio-66@PmPD (1:
0.5), Uio-66@PmPD (1:And Uio-66@PmPD (1 1):3) adsorption capacity of PmPD is respectively 745,680 and 600mg in
g‐1, higher than PmPD particle (415mg g pure in this experiment‐1) and pure PmPD particle (373mg g reported in the literature‐1).This
Show compared with the PmPD particle of suitable size, the configuration of core-shell structure exposes the effective component on outer surface, strengthens suction
Attached site.
Calculate the equation 1 of PmPD load capacity
wPmPDIndicate the mass percent of PmPD, %；Indicate H2O mass loss percentage (<150 DEG C), %；wr
It is the mass percent of residue, %；η is the mass percent that Uio-66 residue accounts for Uio-66, %；
wr(Uio-66) the final residue mass percent of Uio-66 thermogravimetric curve, % are indicated；
Indicate Uio-66 thermogravimetric in moisture loss mass percent (<150 DEG C), %
Calculate the equation 2 of PmPD Cr (VI) adsorbance in compound
QPmPDIndicate the adsorbance of PmPD in compound, mg g‐1；QUio-66@PmPD(1:x)Indicate the adsorbance of compound, mg
g‐1；QUio-66Indicate the adsorbance of Uio-66, mg g‐1；wUio-66Indicate the mass percent of Uio-66 in compound, %；
Table 1 is the comparison of the BET specific surface area of Examples 1 to 3 products therefrom, pore volume and average pore size
1 Uio-66/PmPD (1 of table:X) specific surface area of series composite materials, pore volume, average pore size compare
Increase as seen from table with mPD dosage, the specific surface area of compound is decreased obviously, and hole, which holds, then to be gradually reduced, this can
It can be that the micropore for plugging Uio-66 due to the PmPD of outer layer covers causes.
Specific embodiment：
The present invention is further described with reference to embodiments, without will limit the present invention.
Embodiment 1
Precise 600mg Uio-66 is simultaneously added in the round-bottomed flask of 250ml, and 150ml distilled water is added and stirs and surpasses
Sound dispersion, then precise 300mg m-phenylene diamine (MPD) monomer and 300mg dodecyl sodium sulfate and be added to above-mentioned flask, stirring
16h comes into full contact with it.Precise 900mg sodium peroxydisulfate, which is dissolved in 50ml distilled water, dissolves it sufficiently, and 37ml is taken to make
With.Sodium peroxydisulfate solution is gradually added dropwise in round-bottomed flask within about 15min, initiated oxidation polymerization.Above-mentioned reaction is in room
Continue 5h in warm (about 20 DEG C), reaction system gradually becomes dark brown by white.After reaction, using being centrifugally separating to obtain
(revolving speed is 8000 revs/min), and remaining sodium peroxydisulfate and dodecyl sodium sulfate are washed away with distilled water.Product is in an oven
12 hours dry, gained black solid powder is nanoscale Uio-66/PmPD composite material, is denoted as Uio-66/PmPD-1:
0.5 (PmPD expression poly m-phenylene diamine, 1:The mass ratio that adds of 0.5 expression Uio-66 and fragrant amine monomers is 1:0.5, hereafter
Name and so on).
Embodiment 2
Precise 200mg Uio-66 is simultaneously added in the round-bottomed flask of 250ml, and 150ml distilled water is added and stirs and surpasses
Sound dispersion, then precise 600mg m-phenylene diamine (MPD) monomer and 200mg dodecyl sodium sulfate and be added to above-mentioned flask, stirring
16h comes into full contact with it.Precise 1.8g sodium peroxydisulfate, which is dissolved in 50ml distilled water, dissolves it sufficiently, and 37ml is taken to make
With.Sodium peroxydisulfate solution is gradually added dropwise in round-bottomed flask within about 15min, initiated oxidation polymerization.Above-mentioned reaction is in room
Continue 5h in warm (about 20 DEG C), reaction system gradually becomes dark brown by white.After reaction, using being centrifugally separating to obtain
(revolving speed is 8000 revs/min), and remaining sodium peroxydisulfate and dodecyl sodium sulfate are washed away with distilled water.Product is in an oven
12 hours dry, gained black solid powder is nanoscale Uio-66/PmPD composite material, is denoted as Uio-66/PmPD-1:3.
Embodiment 3
Precise 200mg Uio-66 is simultaneously added in the round-bottomed flask of 250ml, and 150ml distilled water is added and stirs and surpasses
Sound dispersion, then precise 200mg m-phenylene diamine (MPD) monomer and 200mg dodecyl sodium sulfate and be added to above-mentioned flask, stirring
16h comes into full contact with it.Precise 600mg sodium peroxydisulfate, which is dissolved in 50ml distilled water, dissolves it sufficiently, and 37ml is taken to make
With.Sodium peroxydisulfate solution is gradually added dropwise in round-bottomed flask within about 15min, initiated oxidation polymerization.Above-mentioned reaction is in room
Continue 5h in warm (about 20 DEG C), reaction system gradually becomes dark brown by white.After reaction, using being centrifugally separating to obtain
(revolving speed is 8000 revs/min), and remaining sodium peroxydisulfate and dodecyl sodium sulfate are washed away with distilled water.Product is in an oven
12 hours dry, gained black solid powder is nanoscale Uio-66/PmPD composite material, is denoted as Uio-66/PmPD-1:1.
Embodiment 4
Precise 300mg Uio-66 is simultaneously added in the round-bottomed flask of 250ml, and 150ml distilled water is added and stirs and surpasses
Sound dispersion, then 147.06 μ l aniline monomers of accurate measurement, weigh 300mg dodecyl sodium sulfate and are added to above-mentioned flask, stir
16h is mixed, it is come into full contact with.Precise 524mg sodium peroxydisulfate, which is dissolved in 50ml distilled water, dissolves it sufficiently, takes 37ml
It uses.Sodium peroxydisulfate solution is gradually added dropwise in round-bottomed flask within about 15min, initiated oxidation polymerization.Above-mentioned reaction exists
Continue 5h in room temperature (about 20 DEG C).After reaction, using being centrifugally separating to obtain (revolving speed be 8000 revs/min), and with distilling
Remaining sodium peroxydisulfate and dodecyl sodium sulfate are removed in washing.Product is dried 12 hours in an oven, gained yellow solid powder
For nanoscale Uio-66/PANI composite material, it is denoted as Uio-66/PANI-1:0.5 (PANI indicates polyaniline).
Embodiment 5
Precise 300mg Uio-66 is simultaneously added in the round-bottomed flask of 250ml, and 150ml distilled water is added and stirs and surpasses
Sound dispersion, then 155 μ l pyrrole monomers of accurate measurement weigh 300mg dodecyl sodium sulfate and are added to above-mentioned flask, stirring
16h comes into full contact with it.Precise 719mg sodium peroxydisulfate, which is dissolved in 50ml distilled water, dissolves it sufficiently, and 37ml is taken to make
With.Sodium peroxydisulfate solution is gradually added dropwise in round-bottomed flask within about 15min, initiated oxidation polymerization.Above-mentioned reaction is in room
Continue 5h in warm (about 20 DEG C).After reaction, using being centrifugally separating to obtain (revolving speed be 8000 revs/min), and distilled water is used
Wash away remaining sodium peroxydisulfate and dodecyl sodium sulfate.Product is dried 12 hours in an oven, gained beige solid powder
For nanoscale Uio-66/PPY composite material, it is denoted as Uio-66/PPY-1:0.5 (PPY indicates polypyrrole).
Comparative example 1
It is not added with surfactant.Precise 600mg Uio-66 is simultaneously added in the round-bottomed flask of 250ml, is added
The stirring of 150ml distilled water and ultrasonic disperse, then precise 300mg m-phenylene diamine (MPD) monomer are added to above-mentioned flask, stir 16h,
Come into full contact with it.Precise 900mg sodium peroxydisulfate, which is dissolved in 50ml distilled water, dissolves it sufficiently, and 37ml is taken to use.
Sodium peroxydisulfate solution is gradually added dropwise in round-bottomed flask within about 15min, initiated oxidation polymerization.Above-mentioned reaction is in room temperature
Continue 5h in (about 20 DEG C), reaction system gradually becomes dark brown by white.After reaction, using be centrifugally separating to obtain (turn
Speed is 8000 revs/min), and remaining sodium peroxydisulfate is washed away with distilled water.Product is dried 12 hours in an oven, gained black
Solid powder is nanoscale Uio-66/PmPD composite material, is denoted as Uio-66/PmPD-1:(- NSDS is indicated not 0.5-NSDS
Add surfactant, the Uio-66/PmPD-1 with embodiment 1:0.5 is contrasted).
Embodiment 6
It prepares Uio-66/ poly m-phenylene diamine composite material adsorbent (I)
Precise 600mg Uio-66 is simultaneously added in the round-bottomed flask of 250ml, and 150ml distilled water is added and stirs and surpasses
Sound dispersion, then precise 300mg m-phenylene diamine (MPD) monomer and 300mg dodecyl sodium sulfate and be added to above-mentioned flask, stirring
16h comes into full contact with it.Precise 900mg sodium peroxydisulfate, which is dissolved in 50ml distilled water, dissolves it sufficiently, and 37ml is taken to make
With.Sodium peroxydisulfate solution is gradually added dropwise in round-bottomed flask within about 15min, initiated oxidation polymerization.Above-mentioned reaction is in room
Continue 5h in warm (about 20 DEG C), reaction system gradually becomes dark brown by white.After reaction, using centrifuge separation (revolving speed
It is 8000 revs/min) product is obtained, and remaining sodium peroxydisulfate and dodecyl sodium sulfate are washed away with distilled water.Product is drying
12 hours dry in case, gained black solid powder is nanoscale Uio-66/ poly m-phenylene diamine composite material, is denoted as Uio-
66/PmPD‐1:0.5。
It is as follows with the detection mode of Uio-66/ poly m-phenylene diamine composite material absorption Cr (VI) of above-mentioned preparation：
The certain density Cr of 50ml (VI) solution is pipetted into 125ml polytetrafluoroethylene (PTFE) bottle, it is molten with hydrochloric acid and sodium hydroxide
Liquid adjusts pH to certain certain value, then weighs the Uio-66/ poly m-phenylene diamine composite material of 50mg, is placed in Cr (VI) solution,
It is put into oscillation absorption certain time in 30 DEG C of water-baths, is filtered, remaining Cr (VI) is divided light using diphenylcarbazide in filtrate
Degree method is measured, and right back-pushed-type (1) calculates the adsorbance of adsorbent, and the removal rate of Cr (VI) is calculated by formula (2).
Q：The adsorbance (mg/g) of Cr (VI)；q:The removal rate of Cr (VI)；C0：Initial Cr (VI) concentration (mg/L)；C：It inhales
Attached residual Cr (VI) concentration (mg/L)；V：Containing Cr (VI) liquor capacity (L)；W：The quality (g) of adsorbent is added.
Using the Uio-66/ poly m-phenylene diamine composite material of above method preparation as adsorbent, change the first of Cr (VI)
Beginning concentration obtains initial concentration and adsorbance, the relationship of removal rate.
Adsorbance, removal rate when adsorbing certain density Cr (VI) solution according to Uio-66/ poly m-phenylene diamine composite material
With the variation of initial pH, available adsorption reaction carries out obtaining best Cr (VI) solution initial pH value.
Adsorbance, removal rate when adsorbing certain density Cr (VI) solution according to Uio-66/ poly m-phenylene diamine composite material
It changes with time, the adsorption time and adsorbance, the relationship of removal rate of available a certain concentration Cr (VI) solution.
Embodiment 7
It prepares Uio-66/ poly m-phenylene diamine composite material adsorbent (II)
Precise 200mg Uio-66 is simultaneously added in the round-bottomed flask of 250ml, and 150ml distilled water is added and stirs and surpasses
Sound dispersion, then precise 600mg m-phenylene diamine (MPD) monomer and 200mg dodecyl sodium sulfate and be added to above-mentioned flask, stirring
16h comes into full contact with it.Precise 1.8g sodium peroxydisulfate, which is dissolved in 50ml distilled water, dissolves it sufficiently, and 37ml is taken to make
With.Sodium peroxydisulfate solution is gradually added dropwise in round-bottomed flask within about 15min, initiated oxidation polymerization.Above-mentioned reaction is in room
Continue 5h in warm (about 20 DEG C), reaction system gradually becomes dark brown by white.After reaction, using centrifuge separation (revolving speed
It is 8000 revs/min) product is obtained, and remaining sodium peroxydisulfate and dodecyl sodium sulfate are washed away with distilled water.Product is drying
12 hours dry in case, gained black solid powder is nanoscale Uio-66/PmPD composite material, is denoted as Uio-66/PmPD-
1:3。
Embodiment 8
The initial pH value that 50ml concentration is respectively Cr (VI) solution of 50,100,200,300mg/L is adjusted to 2, is weighed
The Uio-66/ poly m-phenylene diamine composite material (I) of 50mg is that adsorbent is added to respectively in Cr (VI) solution, in 30 DEG C of water-baths
Oscillating reactions 12 hours, remaining Cr (VI) was measured using diphenyl carbazide spectrophotometry in filtrate after filtering, knot
Fruit show when the initial concentration of Cr (VI) solution be 50,100,200,300mg/L when, Uio-66/ poly m-phenylene diamine composite material
It (I) is respectively 47.93,90.86,149.59,169.53mg/g to the adsorbance of Cr (VI), removal rate is respectively 98.56%,
98.20%, 78.60%, 61.12%.
Embodiment 9
The initial pH value that 50ml concentration is respectively Cr (VI) solution of 50,100,200,300mg/L is adjusted to 2, is weighed
The Uio-66/ poly m-phenylene diamine composite material (II) of 50mg is that adsorbent is added to respectively in Cr (VI) solution, in 30 DEG C of water-baths
Middle oscillating reactions 12 hours, remaining Cr (VI) is measured using diphenyl carbazide spectrophotometry in filtrate after filtering,
As the result is shown when the initial concentration of Cr (VI) solution is 50,100,200,300mg/L, Uio-66/ poly m-phenylene diamine composite wood
Material (II) gradually rises as 48.19,91.65,186.99,263.69mg/g the adsorbance of Cr (VI), and removal rate is respectively
99.10%, 99.05%, 98.25%, 95.06%.
Comparative example 2,3
The initial pH value that 50ml concentration is respectively Cr (VI) solution of 50,100,200,300mg/L is adjusted to 2, is weighed
50mg is not that adsorbent is added to respectively in Cr (VI) solution with the compound Uio-66 of poly m-phenylene diamine, is vibrated in 30 DEG C of water-baths
Reaction 12 hours, remaining Cr (VI) is measured using diphenyl carbazide spectrophotometry in filtrate after filtering, is as a result shown
Show when the initial concentration of Cr (VI) solution is 50,100,200,300mg/L, Uio-66 is 31.27 to the adsorbance of Cr (VI),
49.65,73.74,78.02mg/g, removal rate are respectively 64.30%, 53.66%, 38.75%, 28.12%.
It can be seen that compound rear material is to Cr's in water body (VI) compared with not compared with the compound Uio-66 of poly m-phenylene diamine
Absorption property greatly improves.
Embodiment 10
The pH value of Cr (VI) solution for adjusting 50ml 300mg/L is respectively：2,3,5, add 50mg Uio-66/ it is poly- between
Phenylenediamine composite material (I) is into Cr (VI) solution, 30 DEG C of 8 hours of oscillation, and remaining Cr (VI) uses in filtrate after filtering
Diphenyl carbazide spectrophotometry is measured, the results showed that when initial pH is 2,3,5, Uio-66/ poly m-phenylene diamine is compound
The adsorbance of material (I) is respectively 143.25,53.32,38.70mg/g.
Embodiment 11
The pH value of Cr (VI) solution for adjusting 50ml 300mg/L is respectively：2,3,5, add 50mg Uio-66/ it is poly- between
Phenylenediamine composite material (II) is into Cr (VI) solution, 30 DEG C of 8 hours of oscillation, and remaining Cr (VI) uses in filtrate after filtering
Diphenyl carbazide spectrophotometry is measured, the results showed that when initial pH is 2,3,5, Uio-66/ poly m-phenylene diamine is compound
The adsorbance of material (I) is respectively 261.85,79.43,49.27mg/g.
Embodiment 12
Weigh 50mg Uio-66/ poly m-phenylene diamine composite material (I) put into 50ml initial concentration be 300mg/L, it is initial
In Cr (VI) solution that pH is 2,30 DEG C of oscillating reactions certain times, remaining Cr (VI) uses hexichol phosphinylidyne in filtrate after filtering
Two hydrazine spectrophotometry are measured.The result shows that change adsorption time be 5 minutes, 10 minutes, 20 minutes, 30 minutes, it is 1 small
When, 2 hours, 5 hours, 8 hours, 12 hours, resulting removal rate difference 22.50%, 24.32%, 27.73%,
32.27%, 36.82%, 40.00%, 41.95%, 47.86%, 61.12%, adsorbance is respectively 63.54,68.67,
78.30、91.13、103.97、112.95、121.29、143.25、169.53mg/g。
Embodiment 13
Weigh 50mg Uio-66/ poly m-phenylene diamine composite material (II) put into 50ml initial concentration be 300mg/L, just
In Cr (VI) solution that beginning pH is 2,30 DEG C of oscillating reactions certain times, remaining Cr (VI) uses hexichol carbon in filtrate after filtering
Two hydrazine spectrophotometry of acyl is measured.The result shows that changing adsorption time is 5 minutes, 10 minutes, 20 minutes, 30 minutes, 1
Hour, 2 hours, 5 hours, 8 hours, 12 hours, resulting removal rate difference 49.55%, 53.64%,
62.50%, 64.55%, 66.59%, 71.36%, 79.32%, 89.48%, 95.06%, adsorbance is respectively 139.91,
151.46、176.49、182.26、188.04、201.51、223.98、261.85、263.69mg/g。
By above embodiments as it can be seen that in such a way that m-phenylene diamine (MPD) monomer is in Uio-66 surface in situ chemical oxidising polymerisation system
Standby Uio-66/ poly m-phenylene diamine composite material is simple and easy, at low cost, and yield is high, and property is stablized.Uio-66/ poly m-phenylene diamine
Composite material is 100mg/L and Cr below up to 263.69mg/g, and for concentration to the maximal absorptive capacity of Cr (VI)
(VI) solution removal rate is a kind of available adsorbent of the processing industry containing Cr (VI) acid waste water of economy up to 99% or more.
Claims (10)
1. a kind of application of Uio-66/ poly aromatic amine composite material in the processing waste water of Cr containing sexavalence, it is characterised in that：Described
For Uio-66/ poly aromatic amine composite material using Uio-66 as core, poly aromatic amine is shell.
2. application according to claim 1, which is characterized in that the Uio-66/ poly aromatic amine composite material to be used for
Handle the acid waste water of the Cr containing sexavalence.
3. application according to claim 2, which is characterized in that the initial concentration of sexavalence Cr is 10- in acid waste water
300mg/L, pH value 1-5.
4. application according to claim 3, which is characterized in that the pH value in sexavalence Cr acid waste water is 2.
5. application according to claim 2, which is characterized in that by the Uio-66/ poly aromatic amine composite material by solid
Liquor ratio is the waste water mixing that 0.02g/L-2g/L is added to the Cr containing sexavalence, and then oscillating reactions is separated by filtration.
6. application according to claim 2, which is characterized in that add the Uio-66/ poly aromatic amine composite material
Waste water to the Cr containing sexavalence mixes, and then oscillating reactions 5-720min, is separated by filtration.
7. application according to claim 1-6, which is characterized in that the Uio-66/ poly aromatic amine composite wood
The preparation method of material includes the following steps, Uio-66, and fragrant amine monomers are added in the solution, stir and evenly mix；Then it is added dropwise
Persulfate aqueous solution, initiated oxidation polymerization reaction, and be persistently stirred to react, it is separated by solid-liquid separation, washs up to Uio-66/ poly aromatic
Amine composite material.
8. application according to claim 7, which is characterized in that the mass ratio of the Uio-66 and fragrant amine monomers are 1:
5~1:0.25；In reaction system, the mass concentration of Uio-66 is 1~10g/L, and the mass concentration of fragrant amine monomers is 1~10g/
L。
9. application according to claim 7, which is characterized in that surfactant is added in the reaction system, it is described
The mass ratio of Uio-66 and surfactant is 1:2~1:0.3.
10. application according to claim 7, which is characterized in that the molar ratio of the persulfate and fragrant amine monomers
It is 1:1~3:1, the concentration of persulfate solution is 0.01~0.5mol/L.
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