CN106750356A - A kind of method that metal-organic framework materials of utilization UiO 66 purify selenium-containing wastewater - Google Patents
A kind of method that metal-organic framework materials of utilization UiO 66 purify selenium-containing wastewater Download PDFInfo
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- CN106750356A CN106750356A CN201710017375.2A CN201710017375A CN106750356A CN 106750356 A CN106750356 A CN 106750356A CN 201710017375 A CN201710017375 A CN 201710017375A CN 106750356 A CN106750356 A CN 106750356A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
- B01J20/223—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
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
Abstract
The present invention relates to the method that the metal-organic framework materials of UiO 66 are used to purify selenium-containing wastewater, the method have the advantages that：The metal-organic framework material good stabilities of UiO 66, specific surface area is big, and the adsorption capacity to selenium is big, and purification rate is fast；The technology using material separating and recovering when clean-up effect it is smaller by being influenceed；Selenium after desorption is easy to be recycled, both completes wastewater treatment, and the recycling of selenium is realized again, kills two birds with one stone, therefore, the metal-organic framework materials of UiO 66 have broad application prospects in terms of the purification of anion.
Description
Technical field
It is to be related to UiO-66 metals organic specifically the invention belongs to the technical field of waste water processing in environmental project
Frame material is used for the method for purifying selenium-containing wastewater.
Background technology
Selenium element is found in the waste vitriol chamber slag of sulfuric acid plant.Due to it, abundance is very low in the earth's crust,
Selenium and tellurium, rhenium etc. are generally known as " rare element " or " dissipated metal ".Selenium has unique light sensitive characteristic, this characteristic make its
Xerography field is most widely used.In recent years, deepening continuously with research, selenium is in electronics, metallurgy, chemistry, glass manufacture etc.
The application of industrial circle is more and more extensive, and also has certain application in agricultural, medical domain.Additionally, selenium is by WHO (joints
State's health organization) one of the trace element of " needed by human " that determines, and it is endowed the good reputation of " life kindling material ".With the Guang ammonia of selenium half
The selenium that sour form is present is the activated centre of various enzymes, so as to participate in the metabolism of organism, hormone control, anti-oxidant etc.
During.But, the lesion that is not enough or excessively can all causing organism of selenium.Selenium intake is not enough, can cause as Keshan disease,
Kaschin-Beck disease etc.；Selenium intake is excessive, then can cause the selenosis even generation of cancer.At present, the main source of selenium contamination is
Agricultural irrigation water, mining activities water and trade effluent etc..
Selenium is primarily present form for selenate (Se (VI)) and selenite (Se (IV)) in waste water.At present more into
Ripe minimizing technology mainly has chemical precipitation method, flocculent precipitation and biological treatment.Chemical precipitation method be use iron content salt or
Aluminium zinc powder can effectively remove the selenite radical ion (SeO in acid waste water as precipitating reagent3 2-), but to selenate radical from
Son (SeO4 2-) removal effect it is unobvious；Flocculent precipitation is by ferrous salt is added in waste water, being converted into soluble selenium
Insoluble material, but this method needs substantial amounts of ferrous salt, and substantial amounts of sludge can be produced；Will be solvable by anaerobic bio-treated
Property the selenium method that is converted into elemental selenium and removes it is although simple and easy to apply, but the clearance of selenium and unstable.
Metal organic frame (MOFs) material is the cross materialses of class I organic-inorganic, and it is by inorganic metal center (gold
Category ion or metal cluster) it is connected with each other by self assembly with the organic ligand of bridging, a class of formation has periodic network knot
The crystalline state porous material of structure.MOFs materials typically have porous, specific surface area big, structure diversity, with unsatuated metal
The features such as site, its specific surface area is general in 1000-10000m2Between/g, porosity can generally achieve material body
More than 50%.Additionally, the metallic ion coordination number at different inorganic metal centers is different, the inorganic central metallic ions of identical exist
It is likely to that different ligancies can be presented in different organic ligand environment；The species of organic ligand is even more varied, its knot
Structure is also rich and varied, also, organic ligand introduces functional group (such as Br, NH easily by the means orientation of rear modification2、CH3
Deng), material is modified and functionalization, therefore, the necks such as absorption, catalysis and the preparation of biomaterial can be widely used in
Domain.Additionally, MOFs materials have unique topological structure, can apply to separate the stereoselectivity of material.MOFs materials
It is applied to that also there is good action effect during catalytic reaction, because the active site position on material can be with catalytic reaction.Therefore,
In recent years, MOFs materials are increasingly becoming the Hot Contents of research.
UiO-66 materials are that, with zirconium as metal center, terephthalic acid (TPA) is the MOFs materials of organic ligand.Because of Zr-O-C keys
Than stronger, therefore the more other MOFs materials of UiO-66 have physically better and chemical stability；UiO-66 series materials have
Larger specific surface area and more functional group, have good absorption property, such as gas (CO to multiple pollutant2、CH4, water
Steam etc.) and organic matter (n-hexane, hexamethylene, dimethylbenzene etc.), however, UiO-66 materials are rarely applied to the suction of zwitterion
It is attached；Additionally, the anion of UiO-66 materials absorption is easily parsed in the basic conditions, this beneficial to material regeneration and it is cloudy from
The recovery of son.
The content of the invention
It is an object of the invention to overcome the shortcomings of the prior art, there is provided a kind of high-efficient purification selenium-containing wastewater
Selenate radical and selenite radical ion method, it is useless containing selenium that the present invention also provides a kind of purification of UiO-66 metal-organic framework materials
The purposes of water.
Of the invention to provide a kind of preparation method of UiO-66 metal-organic framework materials first, the method step is as follows：
1) zirconium chloride (ZrCl is weighed4) in the dimethylformamide (DMF) that is dissolved in, stir 30-40 minutes；
2) terephthalic acid (TPA) (H is weighed2BDC) it is dissolved in DMF, after stirring 15-25 minutes, is added dropwise over the ice of 2-10mL
Acetic acid；
3) above-mentioned two solution is mixed and stirred for 20-30 minutes, makes to be well mixed；
4) it is transferred in the reactor of polytetrafluoroethyllining lining, at a temperature of 120-130 DEG C, sealing reaction 24-30h；
5) after reaction terminates, reactor is naturally cooled into room temperature, pours out supernatant, centrifugation obtains white solid thing
Matter, is then washed 4-6 days with soaked in absolute ethyl alcohol, and 3-4 ethanol solution is changed daily；- 50~-80 DEG C of freeze-drying 2-5 are small
Shi Hou, obtains UiO-66 materials.
Preferably,
Step 1) in, ZrCl4Quality be 0.318-1.59g, the volume of DMF is 9.4-47mL
Step 2) in, H2The quality of BDC is 0.204-1.02g, and the volume of DMF is 9.4-47mL, and the volume of glacial acetic acid is
2-10mL。
The present invention additionally provides a kind of method that utilization above-mentioned material purifies selenium-containing wastewater, methods described includes：
1) pH value of selenium-containing wastewater is adjusted, adsorbent UiO-66 metal-organic framework materials is then put into selenium-containing wastewater
Reaction vessel in；
2) it is sufficiently mixed adsorbent and selenium-containing wastewater；
3) after absorption reaches balance, using the method for filtering, UiO-66 metal-organic framework materials are separated, you can obtain clear
Clear solution to be measured, that is, remove the purified water of selenium：
Wherein：The adsorbent is UiO-66 metal-organic framework materials.
The method that described UiO-66 metal-organic framework materials purify selenium-containing wastewater,
Step 1) in, selenium-containing wastewater concentration is controlled in 1-120mg/L；The pH value for adjusting waste water with NaOH or nitric acid is
5~7；The dosage of adsorbent UiO-66 series metal organic framework materials is 0.1~1.0g/L；
Step 2) in, adsorbent and selenium-containing wastewater temperature control are sufficiently mixed at 15-35 DEG C, the speed of oscillating reactions device is
150-250rpm/min, the reaction time is 1.5-24h；
Step 3) middle separate method, UiO-66 metal-organic framework materials are separated using the method for filtering.
Described UiO-66 metal-organic framework materials are used to purify the purposes of selenium-containing wastewater, are mainly used in purification waste water
In selenium, including selenium-containing wastewater selenate radical and selenite radical ion.
The present invention compared with prior art, has the following advantages：
(1) the UiO-66 metal-organic framework material stability of present invention offer is high (can stable existence, pyrolysis temperature in water
Up to 400 DEG C of degree)；
(2) big (1171m of the UiO-66 metal-organic framework materials specific surface area that the present invention is provided2/ g), be conducive to quick
Plasma selenium in contact water body, the time needed for shortening adsorption equilibrium, the rate of adsorption is fast；
(3) the UiO-66 metal-organic framework materials that the present invention is provided are big to the adsorption capacity of selenium, and purification efficiency is high：UiO-
66 materials for selenous acid and selenic acid saturated extent of adsorption respectively up to 59.9mg/g and 37.3mg/g (in terms of selenium).
(4) after the technology uses material to adsorb pollutant, material easily by filters, divides from water body in a short time
From reuse, clean-up effect is substantially unaffected during reuse；Selenium after desorption is easy to be recycled.Both wastewater treatment is completed, is realized again
The recycling of selenium, kills two birds with one stone.Therefore, UiO-66 metal-organic framework materials have wide application in terms of the purification of selenium
Prospect.
Brief description of the drawings
Fig. 1 is the nitrogen adsorption-desorption isotherm figure of UiO-66 materials in the embodiment of the present invention one；
Fig. 2 is the thermogravimetric curve of UiO-66 materials in the embodiment of the present invention one；
Fig. 3 is suction of the UiO-66 materials to selenite radical (Se (IV)) and selenate radical (Se (VI)) in the embodiment of the present invention one
Attached dynamics figure；
Fig. 4 be in the embodiment of the present invention one UiO-66 materials to selenite radical (Se (IV)) and selenate radical (Se (VI)) etc.
Warm adsorption curve figure；
Fig. 5 is the recycling result that UiO-66 of the present invention purifies selenite radical (Se (IV)) and selenate radical (Se (VI)).
Specific embodiment
The invention will be further described with three examples below in conjunction with the accompanying drawings, but following examples are served only in invention
That holds further illustrates, and can't form limitation of the present invention.
Embodiment one
1) 0.318-1.59gZrCl is weighed4It is dissolved in the dimethylformamide of 9.4-47mL (DMF), 30-40 points of stirring
Clock；
2) terephthalic acid (TPA) (H of 0.204-1.02g is weighed2BDC) it is dissolved in the DMF of 9.4-47mL, 15-25 points of stirring
Zhong Hou, is added dropwise over the glacial acetic acid of 2-10mL；
3) above-mentioned two solution is mixed and stirred for 20-30 minutes, makes to be well mixed；
4) it is transferred in the reactor of polytetrafluoroethyllining lining, at a temperature of 120-130 DEG C, sealing reaction 24-30h；
5) after reaction terminates, reactor is naturally cooled into room temperature, pours out supernatant, centrifugation obtains white solid thing
Matter, is then washed 4-6 days with soaked in absolute ethyl alcohol, and 3-4 ethanol solution is changed daily；- 50~-80 DEG C of freeze-drying 2-5 are small
Shi Hou, obtains UiO-66 materials.
Embodiment two
1) material for preparing embodiment one, dosage is 0.5g/L, is added to the reaction of 20mg/L selenium-containing wastewater concentration
In container, the pH value for adjusting waste water with NaOH or nitric acid is 6 ± 0.2；
2) under the conditions of 25 DEG C, with the velocity fluctuation reaction vessel of 180rpm/min, adsorbent and selenium-containing wastewater is made fully to mix
Close, the reaction time is 12h；
3) after adsorption equilibrium, this material is separated with filtration method, you can the prepare liquid clarified, the selenium concentration in prepare liquid
Determined using inductive coupling plasma emission spectrograph (ICP-OES), obtain remaining selenium concentration for 5.07mg/L (selenous acid
Sodium) and 16.5mg/L (sodium selenate).
Embodiment three
In order to determine material process selenium-containing wastewater effect prepared by embodiment one, the series of factors of simulated wastewater is first carried out
Experiment.Because selenate and selenite are the principal mode of selenium presence in water body, therefore divided with sodium selenate and sodium selenite
Selenium-containing wastewater is not configured.Sorbing material is mixed with simulated wastewater, is fitted into conical flask, vibrated in constant-temperature shaking incubator,
Hybrid reaction is repeated, reacted mixed liquor is separated by filtration, the concentration of selenium in supernatant is determined using ICP-OES.Absorption
Amount computing formula is as follows：
In formula：
qeIt is sorbing material equilibrium adsorption capacity (mg/g)；
C0It is the initial concentration (mg/L) of selenium in solution；
CeIt is the equilibrium concentration (mg/L) of selenium in solution；
V is liquor capacity (L)；
M is sorbing material quality (g)；
After due to UiO-66 metal-organic framework materials absorption selenium, can be separated by filtration, while the selenium of absorption is also therewith
Separate, reach the purification of selenium in water body.Therefore, purification selenium is represented to the adsorbance of selenium using UiO-66 metal-organic framework materials
Performance.Adsorbance is bigger, it was demonstrated that its clean-up effect is better.
Influence of the selenium-containing wastewater of different affecting factors to UiO-66 adsorbances
(1) influence of the reaction time to UiO-66 absorption selenium-containing wastewaters
PH initial to 20mL is that 6 ± 0.2, concentration is 20mg/L containing sub- selenium to the material prepared with 0.01g embodiments 1 respectively
Sour sodium and sodium selenate simulated wastewater carry out adsorption reaction, wherein reaction time control 1,5,10,20,30,60,90,120,
240th, 360,480,600,720min, after mixed liquor is separated by filtration, determines selenium concentration in supernatant.Under the differential responses time,
The adsorption rate of plasma selenium is as shown in Figure 3.From the figure 3, it may be seen that sorbing material of the invention is fast to plasma selenium adsorption rate, in reaction
Adsorption equilibrium is basically reached after 1.5h.
(2) influence of the initial concentration of selenium-containing wastewater to UiO-66 adsorbances
The concentration of sodium selenate and sodium selenite simulated wastewater in terms of selenium, takes 8 parts of concentration respectively 5mg/L, 10mg/L,
The sodium selenate waste water 20mL of 20mg/L, 40mg/L, 60mg/L, 80mg/L, 100mg/L, 120mg/L；8 parts of concentration are respectively 5mg/
The sodium selenite waste water 20mL of L, 10mg/L, 20mg/L, 40mg/L, 60mg/L, 80mg/L, 100mg/L, 120mg/L, load from
In heart pipe, while being separately added into 0.01g UiO-66, the pH value that waste water is adjusted with NaOH or nitric acid is 6 ± 0.2,25
DEG C, under rotating speed 180rpm/min, adsorption time 12h after mixed liquor is separated by filtration, determines selenium concentration in supernatant.It was found that with
Sodium selenate and concentration of sodium selenite rises, adsorbance also constantly increases.Its maximal absorptive capacity is：UiO-66 is for sodium selenite
With the saturated extent of adsorption of sodium selenate respectively up to 59.9mg/g and 37.3mg/g, in terms of selenium.(shown in accompanying drawing 4)
(3) UiO-66 reuses influence of the number of times to selenium-containing wastewater purifying rate
It is 20mg/L containing sodium selenate, sodium selenite waste water 20mL respectively to take 1 part of concentration, is separately added into 0.01g UiO-66,
The pH value that waste water is adjusted with NaOH or nitric acid is 6 ± 0.2, and at 25 DEG C, under 180rpm/min rotating speeds, adsorption time 12h is mixed
After conjunction liquid is centrifuged, selenium concentration in supernatant is determined, the UiO-66 of separation adds the NaOH solution regulation of 0.1mol/L molten
The pH value of liquid carries out desorption, scrubbed rear reuse for 8.5 ± 0.2.It was found that after 5 times circulate, for Selenium in Wastewater
Adsorbance remain at more than the 90% of first adsorbance.(shown in accompanying drawing 5)
(4) UiO-66 adsorbs the contrast of selenium with other adsorbents
As can be seen from the above table, UiO-66 has preferably suction in the case where dosage is low to two kinds of valence states of selenium
Attached effect, hence it is evident that better than other materials.
The preparation of above-mentioned UiO-66 materials, is not limited only to the method described in the present embodiment, can be with purchased in market or use it
The method that he prepares UiO-66 metal-organic framework materials.
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Claims (5)
1. a kind of method for preparing UiO-66 metal-organic framework materials, it is characterised in that methods described includes：
1) zirconium chloride (ZrCl is weighed4) be dissolved in dimethylformamide (DMF), stir 30-40 minutes；
2) terephthalic acid (TPA) (H is weighed2BDC) it is dissolved in DMF, after stirring 15-25 minutes, is added dropwise over the glacial acetic acid of 2-10mL；
3) above-mentioned two solution is mixed and stirred for 20-30 minutes, makes to be well mixed；
4) it is transferred in the reactor of polytetrafluoroethyllining lining, at a temperature of 120-130 DEG C, sealing reaction 24-30h；
5) after reaction terminates, reactor is naturally cooled into room temperature, pours out supernatant, centrifugation obtains white solid matter, so
Washed 4-6 days with soaked in absolute ethyl alcohol afterwards, 3-4 ethanol solution is changed daily；- 50~-80 DEG C after freeze-drying 2-5 hours,
Obtain UiO-66 materials.
2. the method for preparing UiO-66 metal-organic framework materials according to claim 1, it is characterised in that；
Step 1) in, ZrCl4Quality be 0.318-1.59g, the volume of DMF is 9.4-47mL；
Step 2) in, H2The quality of BDC is 0.204-1.02g, and the volume of DMF is 9.4-47mL, and the volume of glacial acetic acid is 2-
10mL。
3. a kind of method that utilization UiO-66 metal-organic framework materials purify selenium-containing wastewater, it is characterised in that the method includes：
1) pH value of selenium-containing wastewater is adjusted, in then adding an adsorbent into the reaction vessel of selenium-containing wastewater；
2) it is sufficiently mixed adsorbent and selenium-containing wastewater；
3) after absorption reaches balance, using the method for filtering, separating adsorbent, you can the solution to be measured clarified removes selenium
Purified water；
Wherein：
The adsorbent is UiO-66 metal-organic framework materials.
4. it is according to claim 3 purification selenium-containing wastewater method, it is characterised in that；
Step 1) in, selenium-containing wastewater concentration is controlled in 1-120mg/L；With NaOH or nitric acid adjust the pH value of waste water for 5~
7, the dosage of adsorbent is 0.1~1.0g/L；
Step 2) in, it is sufficiently mixed adsorbent and selenium-containing wastewater, at 15-35 DEG C, the speed of oscillating reactions device is temperature control
150-250rpm/min, the reaction time is 1.5-24h；
Step 3) middle separate method, using the method separating adsorbent of filtering.
5.UiO-66 series metals organic framework materials are used to purify the purposes of selenium-containing wastewater, and the purposes is：It is applied to removal
Selenium in waste water, including selenium-containing wastewater selenate radical and selenite radical ion.
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