CN105923738A - Method for utilizing metal organic skeleton to carry out efficient catalytic activation on persulfate or peroxymonosulfate to process organic wastewater - Google Patents
Method for utilizing metal organic skeleton to carry out efficient catalytic activation on persulfate or peroxymonosulfate to process organic wastewater Download PDFInfo
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- CN105923738A CN105923738A CN201610451055.3A CN201610451055A CN105923738A CN 105923738 A CN105923738 A CN 105923738A CN 201610451055 A CN201610451055 A CN 201610451055A CN 105923738 A CN105923738 A CN 105923738A
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
Abstract
The invention discloses a method for utilizing a metal organic skeleton to carry out efficient catalytic activation on persulfate or peroxymonosulfate to process organic wastewater. According to the method, a metal organic skeleton material is used as a catalyst, and the characteristics of high active site and high catalytic activity of the metal organic skeleton are used for carrying out catalytic activation on persulfate or peroxymonosulfate to generate sulfate free redical under a condition of normal temperature to degrade organic pollutants in the organic wastewater. The catalyst is easy in recovering and reusing, the activation effect of the catalyst is still good after the catalyst is reused for multiple times, and the catalyst is an environment-friendly material. The method is suitable for processing various types of organic wastewater, has the advantages of good durability, short catalysis time and convenience in operation, has a good degradation effect within a wide PH (Potential of Hydrogen) range, and has a large application prospect on an aspect of the degradation of water body organic pollutants.
Description
Technical field
The invention belongs to the oxidation technology field of organic pollutants, be specifically related under a kind of room temperature utilize metal
Organic backbone efficient catalytic activation persulfate or the method for hydrogen persulfate salt treatment organic wastewater.
Background technology
Water pollution control be current environmental protection personnel research theme, water pollution be face of mankind nowadays serious crisis it
One, control water pollution, especially control poisonous and harmful organic contamination in water body, be the emphasis of engineering of water treatment research, be also
Difficult point.High-level oxidation technology based on potentiometric titrations (SO4), due to the high efficiency of its degradation of contaminant, is come by more
The concern of the most researcheres and attention.In existing report, persulfate is produced potentiometric titrations and typically uses light
Activation, thermal activation, the ultrasonic and activation of metal ion.But there is the shortcomings such as high, the generation mud of cost and make in these technology
Extensively application it is difficult in real life.And utilize metallic organic framework as heterogeneous catalysis catalysis persulfate or over cure
Acid hydrogen salt produces sulfate ion and overcomes these shortcomings, and it is excellent to have height reusable, active, excellent catalytic effect etc.
Gesture, becomes the focus of current researcher research.
Metal-organic framework materials (MOFs) is that a class is obtained by Coordinate self-assembly by metal node and organic ligand
There is the crystalline state porous material of regular pore canal or void structure.This material has higher specific surface area, abundant duct knot
Structure and higher physical and chemical stability, easily load other materials and do not change itself structure, add metallic organic framework
Containing substantial amounts of unsaturated coordinating metal node so that it is be catalyzed, separate, the aspect such as absorption shows excellent serviceability.
The present invention utilizes metal-organic framework materials MIL-88A be catalyzed persulfate at normal temperatures or persulfuric acid hydrogen salt produces sulfate radical
Ionic degradation industrial organic waste water, catalyst recycles respond well, decreases operating cost, and this material is imitated at normal temperatures
Fruit has reached more than 90%, and PH applied range, provides, for processing organic wastewater, the prospect of being widely applied.
Summary of the invention
It is an object of the invention to for homogeneous catalysts such as existing ferrous ion, Zero-valent Iron in activation persulfate system
Middle there is the problem that ferrous ion easily lost efficacy, can not recycle and produce iron cement, it is proposed that one at normal temperatures can be high
The heterogeneous catalysis of effect degradation of organic waste water.This catalyst has that consumption is few, equipment is simple and convenient to operate, cheap with
And the advantage being suitable for PH scope wide (2 ~ 9).
The purpose of the present invention one of at least adopts the following technical scheme that and to realize:
A kind of utilize metallic organic framework efficient catalytic activation persulfate or the method for hydrogen persulfate salt treatment organic wastewater, with
Metal-organic framework materials is catalyst, utilizes the feature that metallic organic framework avtive spot is high and catalysis activity is strong, often
In the organic wastewater containing organic pollution, add persulfate or persulfuric acid hydrogen salt and metallic organic framework under temperature in the lump, make
Persulfate or persulfuric acid hydrogen salt produce strong oxidizing property under the metallic organic framework catalytic action as heterogeneous catalysis
Potentiometric titrations, potentiometric titrations aoxidizes the organic pollution in water further, makes organic pollutant degradation, improves water
Matter environment.
Further, described metallic organic framework be the mode of appearance of MIL-88A, MIL-88A be that hexagonal is shaft-like, specific surface
Amassing is 10 ~ 30m2/g。
Further, the preparation method of described metallic organic framework MIL-88A comprises the steps:
(1) fumaric acid and FeCl are taken respectively3·6H2O mol ratio is that 1:10 ~ 20:1 is dissolved in the deionized water of 42 ~ 50ml, warp
After crossing the stirring of 1 ~ 2 hour, the solution stirred is transferred in teflon-lined reactor, reactor is placed
In air dry oven, take out reactor after reacting 2 ~ 12h at 65 ~ 105 DEG C, reactor is cooled to room temperature；
(2) reactor cooling after, mixture reacted in still is transferred to centrifuge tube, under the conditions of 8000 ~ 10000rpm from
The heart 10 ~ 12min isolated faint yellow solid；Subsequently faint yellow solid is poured in beaker, after washing with alcohol 2h ~ 3h, from
The heart, then it is washed with deionized 2h ~ 3h, it is repeated twice, obtains wet metallic organic framework MIL-88A solid；By wet metal
Vacuum drying oven put into by organic backbone MIL-88A solid, is dried 8 ~ 12h at 80 ~ 120 DEG C, obtains described metallic organic framework
MIL-88A。
Further, described organic wastewater PH is 2 ~ 9, and catalytic reaction is carried out under normal temperature condition.
Further, prepared metallic organic framework MIL-88A and persulfate or persulfuric acid hydrogen salt are joined in the lump
In organic wastewater, under normal temperature condition, reacting in rotating speed is 50 ~ 500 rpm shaking tables, sample is also carried out point by spot sampling
Analysis, the response time is 30 ~ 150min.
Further, described persulfate includes more than one in sodium peroxydisulfate, potassium peroxydisulfate and Ammonium persulfate., institute
The persulfuric acid hydrogen salt stated includes more than one in potassium hydrogen persulfate, hydrogen persulfate sodium and hydrogen persulfate ammonium.
Further, the organic dirt in the persulfate added in organic wastewater or persulfuric acid hydrogen salt and organic wastewater
The mol ratio of dye thing is 20:1 ~ 100:1.
Further, the dosage of described metallic organic framework MIL-88A is 0.05 ~ 0.6 g/L.
Further, described metallic organic framework MIL-88A, through recycled for multiple times, embodies metallic organic framework
The catalytic capability that MIL-88A is maximum.
Compared with prior art, the invention have the advantages that and technique effect:
(1) preparation method of the metallic organic framework MIL-88A that the present invention provides, simple to operate, and preparation condition is gentle, repeats behaviour
The property made is relatively strong, easily realizes；
(2) this metallic organic framework has more pore structure and undersaturated metal active centres, enhances persulfate
Or persulfuric acid hydrogen salt produces the effect of potentiometric titrations, this catalyst is good to the removal effect of pollutant；
(3) heterogeneous catalysis of the present invention is to target contaminant non-selectivity, and the suitability is extensive；
(4) catalyst of the present invention can utilize with repetitive cycling, environmental friendliness, non-secondary pollution；
(5) to be suitable for PH scope wide for catalyst of the present invention；
(6) method of the present invention need not consume additional energy, including ultrasonic, light and electricity, reduces cost；And technological process
Very simple, workable, persistency is good, and catalysis time is short, has actual application prospect extensively.
Accompanying drawing explanation
Fig. 1 be preparation condition be the X-ray crystal diffraction of 2h/65 DEG C of prepared metal-organic framework materials MIL-88A
Figure (XRD)；
Fig. 2 be preparation condition be the scanning electron microscope (SEM) photograph (SEM) of 2h/65 DEG C of prepared metal-organic framework materials MIL-88A.
Detailed description of the invention
Below by embodiment, the invention will be further described, illustrates outstanding feature and the marked improvement of the present invention, only
Indicate that the present invention is in no way limited to following instance.
The present invention is typical organic wastewater with dyestuff orange G (OG), in order to prove the present invention nothing to target contaminant
Selectivity, also have selected rhodamine B and acid orange AO7As target contaminant.
Case study on implementation 1:
The implementation case is that research MIL-88A is for the fall of OG with the 2h/65 DEG C of MIL-88A catalyst prepared for preparation condition
Solve effect.
(1) preparation of metallic organic framework MIL-88A: weigh 0.9744g(1mol) fumaric acid and 2.2722g(1mol)
FeCl3·6H2O is dissolved in the deionized water of 42ml, after the stirring of 1 hour, transfers the solution into the polytetrafluoro of 100ml
In the reactor of ethylene liner, reactor is placed in air dry oven, after reacting 2h at 65 DEG C, takes out reactor, will be anti-
Still is answered to cool down to room temperature.After reactor cooling, being taken out by reacted mixture, under the conditions of 9000rpm, centrifugal 10min separates
Obtain faint yellow solid, subsequently faint yellow solid is poured in beaker, after washing with alcohol 3h, centrifugal, then be washed with deionized water
Wash 3h, be repeated twice, after obtaining solid, put into vacuum drying oven at 100 DEG C of dry 8h.Obtain described metallic organic framework
MIL-88A, and give over to standby；
The X-ray crystallogram (XRD) of the metallic organic framework MIL-88A obtained is as it is shown in figure 1, can learn this sample from figure
Product crystalline structure structure is preferable, and degree of crystallinity is higher.Fig. 2 is the scanning electron microscope (SEM) photograph of the metallic organic framework MIL-88A obtained
(SEM), the mode of appearance of metallic organic framework MIL-88A is that hexagonal is shaft-like as seen from Figure 2, and not of uniform size.
(2) Na of 100mmol/L is prepared2S2O8Solution, the OG solution for standby of 10mmol/L；
(3) using conical flask is reactor, adds 100mmol/LNa in reactor2S2O8 6mL and 10mmol/LOG 1mL
(nNa2S2O8/ nOG=60) and deionized water to keep in reactor, the volume of solution is as 100mL, simultaneously toward throwing in reactor
Add 0.03g metal-organic framework materials, regulate PH=2.8, conical flask is placed in the shaking table of 200rpm, under normal temperature condition
React, spot sampling analysis；
(4) being added without metal-organic framework materials MIL-88A in the reactor, other conditions are with (3)；
(5) Na it is added without in the reactor2S2O8Solution, other conditions are with (3)；
The clearance of three kinds of techniques is as shown in table 1.
Table 1: metallic organic framework MIL-88A is for the absorption degradation effect of OG
| Time (min) | Clearance %(3) | Clearance %(4) | Clearance %(5) |
| 0 | 0.0 | 0.0 | 0.0 |
| 10 | 11.6 | 0.6 | 1.9 |
| 20 | 23.2 | 0.9 | 2.5 |
| 30 | 30.4 | 1.2 | 3.4 |
| 40 | 41.2 | 1.5 | 4.3 |
| 50 | 52.3 | 1.8 | 4.9 |
| 60 | 66.9 | 2.4 | 5.8 |
| 90 | 78.8 | 3.1 | 5.8 |
| 120 | 90.4 | 3.4 | 7.1 |
As shown in Table 1: it is the most weak to the removal effect of OG to be used alone metallic organic framework MIL-88A or sodium peroxydisulfate, but work as
When being simultaneously introduced metallic organic framework MIL-88A and sodium peroxydisulfate, the clearance of OG significantly improves.
Case study on implementation 2:
The implementation case be the MIL-88A prepared with 2h/65 DEG C of preparation condition as catalyst, study Na2S2O8Mol ratio with OG
Different (nNa2S2O8/ nOG=20,40,60,80,100) for catalytic activation reaction impact.
(1) preparation method of metallic organic framework MIL-88A is with the step (1) in case study on implementation 1；
(2) Na of 100mmol/L is prepared2S2O8Solution, the OG solution for standby of 10mmol/L；
(3) using conical flask is reactor, adds 100mmol/LNa in reactor2S2O8 2mL and 10mmol/LOG 1mL
(nNa2S2O8/ nOG=20) and deionized water to keep in reactor, the volume of solution is as 100mL, simultaneously toward throwing in reactor
Add 0.03g metal-organic framework materials MIL-88A, regulate PH=2.8, conical flask is placed in the shaking table of 300rpm, at room temperature
Under the conditions of react, spot sampling analysis；
(4) in reactor, 100mmol/LNa is added2S2O8 4mL and 10mmol/LOG 1mL(nNa2S2O8/ nOG=40) and
The volume of solution is as 100mL to keep in reactor for deionized water, and other conditions are with (3).
(5) in reactor, 100mmol/LNa is added2S2O8 6mL and 10mmol/LOG 1mL(nNa2S2O8/ nOG=60)
And deionized water is so that in holding reactor, the volume of solution is as 100mL, other conditions are with (3).
(6) in reactor, 100mmol/LNa is added2S2O8 8mL and 10mmol/LOG 1mL(nNa2S2O8/ nOG=80)
And deionized water is so that in holding reactor, the volume of solution is as 100mL, other conditions are with (3).
(7) in reactor, 100mmol/LNa is added2S2O8 10mL and 10mmol/LOG 1mL(nNa2S2O8/nOG=
100) and deionized water to keep in reactor, the volume of solution is as 100mL, other conditions are with (3).
Five kinds of technique clearances are as shown in table 2.
Table 2: different nNa2S2O8/ nOG adds the comparison being compared to OG degradation effect
As shown in Table 2: along with nNa2S2O8/ nOG ratio increases, and reaction clearance presents ascendant trend, but when ratio arrival 60:
After 1, the change of clearance is little, all more than 90%, from the standpoint of reaction efficiency and cost, and nNa2S2O8/ nOG=60 is
Optimum selection.
Case study on implementation 3
The implementation case be the MIL-88A prepared with 2h/65 DEG C of preparation condition as catalyst, the dosage of research MIL-88A
The impact that (0.005g, 0.01g, 0.02g, 0.03g, 0.04g, 0.05g, 0.06g) reacts for catalytic activation.
(1) preparation method of metallic organic framework MIL-88A is with the step (1) in case study on implementation 1；
(2) Na of 100mmol/L is prepared2S2O8Solution, the OG solution for standby of 10mmol/L；
(3) using conical flask is reactor, adds 100mmol/LNa in reactor2S2O86mL and 10mmol/LOG 1mL
(nNa2S2O8/ nOG=60) and deionized water to keep in reactor, the volume of solution is as 100mL, simultaneously toward throwing in reactor
Add 0.005g metal-organic framework materials MIL-88A, regulate PH=2.8, conical flask is placed in the shaking table of 500rpm, often
React under the conditions of temperature, spot sampling analysis；
(4) adding 0.01g metal-organic framework materials MIL-88A in reactor, other conditions are with (3)；
(5) adding 0.02g metal-organic framework materials MIL-88A in reactor, other conditions are with (3)；
(6) adding 0.03g metal-organic framework materials MIL-88A in reactor, other conditions are with (3)；
(7) adding 0.04g metal-organic framework materials MIL-88A in reactor, other conditions are with (3)；
(8) adding 0.05g metal-organic framework materials MIL-88A in reactor, other conditions are with (3)；
(9) adding 0.06g metal-organic framework materials MIL-88A in reactor, other conditions are with (3)；Going of seven kinds of techniques
Except rate is as shown in table 3 below.
Table 3: the effect of different metal organic backbone MIL-88A dosage degraded OG
As shown in Table 3: when 150min, the dosage of MIL-88A be 0.005g, 0.01g, 0.02g, 0.03g, 0.04g,
When 0.05g, 0.06g, the degradation efficiency to OG is respectively 83.3%, 87.6%, 92.3%, 98.0%, 94.0%, 92.1%, 89.4%.By
This is visible, and along with catalyst amounts is increasing, degradation efficiency rose before this, after catalyst amounts reaches 0.03g
Present downward trend, when the dosage of MIL-88A is 0.03g, best to the degradation effect of OG, it is optimum selection.
Case study on implementation 4:
The implementation case is that the metal of the different preparation time (2h, 6h, 12h) of research or temperature (65 DEG C, 85 DEG C, 105 DEG C) is organic
The impact that skeleton MIL-88A reacts for catalytic activation.
(1) preparation method of the metallic organic framework MIL-88A of different preparation times is as follows: weigh 0.9744g
(1mol) fumaric acid and 22.722g(10mol) FeCl3 6H2O is dissolved in the deionized water of 50ml, through the stirring of 2 hours
After, transfer the solution in the teflon-lined reactor of 100ml, reactor is placed in air dry oven,
Take out reactor after reacting 2h, 6h, 12h at 65 DEG C respectively, reactor to room temperature is cooled down.After reactor cooling, after reacting
Mixture take out, under the conditions of 9000rpm, centrifugal 10min isolated faint yellow solid, pours into faint yellow solid subsequently
In beaker, after washing with alcohol 3h, centrifugal, then it is washed with deionized 3h, it is repeated twice, after obtaining solid, puts into vacuum and do
Dry case is at 100 DEG C of dry 8h, and gained is described metallic organic framework MIL-88A, and gives over to standby；
(2) preparation method of the metallic organic framework MIL-88A of different preparation temperatures is as follows: weigh 19.488g(20mol)
Fumaric acid and 2.2722g(1mol) FeCl3 6H2O is dissolved in the deionized water of 46ml, after the stirring of 1.5 hours, will
Solution is transferred to, in the teflon-lined reactor of 100ml, be placed in air dry oven by reactor, respectively 65
DEG C, 85 DEG C, react 2h at 105 DEG C after take out reactor, reactor to room temperature is cooled down.After reactor cooling, by reacted
Mixture takes out, and under the conditions of 9000rpm, centrifugal 10min isolated faint yellow solid, pours faint yellow solid into burning subsequently
In Bei, after washing with alcohol 3h, centrifugal, then it is washed with deionized 3h, it is repeated twice, after obtaining solid, puts into vacuum drying
Case is at 100 DEG C of dry 8h, and gained is described metallic organic framework MIL-88A, and gives over to standby；
(3) Na of 100mmol/L is prepared2S2O8Solution, the OG solution for standby of 10mmol/L；
(4) using conical flask is reactor, adds 100mmol/LNa in reactor2S2O86mL and 10mmol/LOG 1mL
(nNa2S2O8/ nOG=60) and deionized water to keep in reactor, the volume of solution is as 100mL, simultaneously toward throwing in reactor
The metallic organic framework MIL-88A prepared under the conditions of adding 0.03g 2h/65 DEG C, regulates PH=2.8, conical flask is placed on 50rpm
Shaking table in, react under normal temperature condition, spot sampling analysis；
(5) the metallic organic framework MIL-88A of preparation under the conditions of adding 2h/85 DEG C in reactor, other conditions are with (4)；
(6) the metallic organic framework MIL-88A of preparation under the conditions of adding 2h/105 DEG C in reactor, other conditions are with (4)；
(7) the metallic organic framework MIL-88A of preparation under the conditions of adding 6h/65 DEG C in reactor, other conditions are with (4)；
(8) the metallic organic framework MIL-88A of preparation under the conditions of adding 12h/65 DEG C in reactor, other conditions are with (4)；
The clearance of the metallic organic framework MIL-88A that five kinds of technique obtains is as shown in table 4.
Table 4: the metallic organic framework MIL-88A of the preparation degradation effect to OG under different time or temperature conditions
As shown in Table 4: after 150min, 2h/65 DEG C, 2h/85 DEG C, the metallic organic framework of preparation under the conditions of 2h/105 DEG C
MIL-88A is 95.7%, 96.4%, 85.7% to the degradation effect of OG respectively.Understanding when preparation time is 2h, preparation temperature is
When 85 DEG C, degradation effect is optimal, and along with temperature raises, degradation effect has declined.After 150min, 2h/65 DEG C, 6h/65 DEG C,
Under the conditions of 12h/65 DEG C, the metallic organic framework MIL-88A of preparation is 95.7%, 68%, 47% to the degradation effect of OG respectively.Visible
When preparation temperature one timing, along with the prolongation of preparation time, metallic organic framework MIL-88A presents decline to the degradation effect of OG
Trend, effectively shortens catalyst preparation time.
Case study on implementation 5:
The implementation case be the metallic organic framework MIL-88A prepared with 2h/65 DEG C of preparation condition as catalyst, study Industry Waste
In water, PH is for the impact of the OG that degrades.
(1) preparation method of metallic organic framework MIL-88A is with the step (1) in case 1；
(2) Na of 100mmol/L is prepared2S2O8Solution, the OG solution for standby of 10mmol/L；
(3) using conical flask is reactor, adds 100mmol/LNa in reactor2S2O86mL and 10mmol/LOG 1mL
(nNa2S2O8/ nOG=60) and deionized water to keep the volume in reactor as 100mL, add in reactor simultaneously
0.03g metal-organic framework materials MIL-88A, the PH=2 in regulation reactor, be placed on conical flask in the shaking table of 200rpm,
React under normal temperature condition, spot sampling analysis；
(4) PH=3 of solution in regulation reactor, other conditions are with (3)；
(5) PH=4 of solution in regulation reactor, other conditions are with (3)；
(6) PH=5 of solution in regulation reactor, other conditions are with (3)；
(7) PH=7 of solution in regulation reactor, other conditions are with (3)；
(8) PH=9 of solution in regulation reactor, other conditions are with (3)；
The clearance of six kinds of techniques is as shown in table 5.
Table 5: degradation effect to OG under the conditions of different PH
As shown in Table 5: although during PH ＞ 7, when clearance is not as PH ＜ 7, but having certain clearance, illustrating that this metal has
Machine skeleton MIL-88A has degradation effect in wide PH scope, simply increases along with PH, and degradation effect declines.
Case study on implementation 6:
The implementation case be the MIL-88A prepared with 2h/65 DEG C of preparation condition as catalyst, the recycling of research MIL-88A
Impact for degraded OG reaction.
(1) preparation method of metallic organic framework MIL-88A is with the step (1) in case 1；
(2) Na of 100mmol/L is prepared2S2O8Solution, the OG solution for standby of 10mmol/L；
(3) using conical flask is reactor, adds 100mmol/LNa in reactor2S2O86mL and 10mmol/LOG 1mL
(nNa2S2O8/ nOG=60) and deionized water to keep the volume in reactor as 100mL, add in reactor simultaneously
0.03g metal-organic framework materials MIL-88A, regulates PH=2.8, conical flask is placed in the shaking table of 200rpm, at room temperature bar
React under part, pinpoint analytical sampling；
(4), after step (3) terminates, the catalyst high speed centrifugation inside conical flask is separated, puts into after drying in 65 DEG C of baking ovens
In the reaction system identical with the system of (3), other conditions are with (3)；
(5) according to the method for (3) Yu (4).Catalyst recycles through four times, each the circulation result such as table to OG clearance
Shown in 6.
Tetra-circulations of table 6:MIL-88A are compared for the removal effect of degraded OG
| Time (min) | Clearance %(1st) | Clearance %(2nd) | Clearance %(3rd) | Clearance %(4th) |
| 0 | 0.0 | 0.0 | 0.0 | 0.0 |
| 20 | 25.6 | 46.4 | 37.1 | 25.2 |
| 40 | 42.8 | 69.0 | 57.4 | 42.0 |
| 60 | 59.7 | 81.8 | 70.8 | 55.9 |
| 90 | 79.1 | 92.0 | 84.7 | 69.2 |
| 120 | 89.5 | 95.3 | 89.9 | 79.4 |
| 150 | 94.5 | 96.2 | 93.5 | 87.5 |
As shown in Table 6: after four circulations, and in the case of catalyst is lossy, metallic organic framework MIL-88A is for degraded
The clearance of OG is still maintained at more than 85%, illustrates that the reusable edible of MIL-88A is good.
Case study on implementation 7:
The implementation case be the MIL-88A prepared with 2h/65 DEG C of preparation condition as catalyst, research MIL-88A is for degraded not
Same pollutant (orange G, rhodamine B, acid orange AO7) impact.
(1) preparation method of metallic organic framework MIL-88A is with step (1) in case study on implementation 1；
(2) Na of 100mmol/L is prepared2S2O8Solution, the OG solution of 10mmol/L, 10mmolRhB solution, 10mmol/LAO7Molten
Liquid is standby；
(3) using conical flask is reactor, adds 100mmol/LNa in reactor2S2O86mL and 10mmol/LOG 1mL
(nNa2S2O8/nOG=60) and deionized water to keep in reactor, the volume of solution is as 100mL, simultaneously toward throwing in reactor
Add 0.03g metal-organic framework materials MIL-88A, regulate PH=2.8, conical flask is placed in the shaking table of 300rpm, at room temperature
Under the conditions of react, spot sampling analysis；
(4) adding 10mmol/L RhB 1mL in reactor, other conditions are with (3)；
(5) in reactor, 10mmol/L AO is added71mL, other conditions are with (3)；
The clearance of three kinds of techniques is as shown in table 7.
The table 7:MIL-88A degradation effect contrast to different pollutant
| Time (time) | Clearance %(OG) | Clearance %(RhB) | Clearance %(AO7) |
| 0 | 0.0 | 0.0 | 0.0 |
| 30 | 30.4 | 31.5 | 29.8 |
| 60 | 55.8 | 60.2 | 53.4 |
| 90 | 76.5 | 80.4 | 75 |
| 120 | 92.5 | 95.3 | 90.6 |
| 150 | 98.0 | 99.8 | 95.5 |
As shown in Table 7: after 150min, MIL-88A 98% be respectively for the degradation efficiency of OG, RhB and AO7,99.8%,
95.5%, it can be seen that MIL-88A is suitable for the clearance of different pollutant, illustrate MIL-88A for pollutant without selection
Property, can effectively remove Some Organic Pollutants.
Claims (10)
1. utilize metallic organic framework efficient catalytic activation persulfate or a method for hydrogen persulfate salt treatment organic wastewater,
It is characterized in that: use metallic organic framework as heterogeneous catalysis, utilize the unsaturation of metallic organic framework avtive spot
Coordination center, puts in organic wastewater with persulfate or persulfuric acid hydrogen salt in the lump by metallic organic framework under normal temperature condition,
Metallic organic framework produces potentiometric titrations by catalysis persulfate or persulfuric acid hydrogen salt, and potentiometric titrations is to organic waste
Organic pollution in water carries out oxidative degradation, improves water quality environment.
One the most according to claim 1 utilizes metallic organic framework efficient catalytic activation persulfate or persulfuric acid hydrogen salt
Process organic wastewater method, it is characterised in that: described metallic organic framework be the mode of appearance of MIL-88A, MIL-88A be six
Angular pole shape, specific surface area is 10 ~ 30m2/g。
One the most according to claim 2 utilizes metallic organic framework efficient catalytic activation persulfate or persulfuric acid hydrogen salt
The method processing organic wastewater, it is characterised in that the preparation method of described metallic organic framework MIL-88A is as follows:
(1) fumaric acid and FeCl are taken respectively3·6H2O mol ratio is that 1:10 ~ 20:1 is dissolved in the deionized water of 42 ~ 50ml, passes through
After the stirring of 1 ~ 2 hour, transfer to the solution stirred, in teflon-lined reactor, be placed on by reactor
In air dry oven, take out reactor after reacting 2 ~ 12h at 65 ~ 105 DEG C, reactor is cooled to room temperature；
(2) reactor cooling after, mixture reacted in still is transferred to centrifuge tube, under the conditions of 8000 ~ 10000rpm from
The heart 10 ~ 12min isolated faint yellow solid；Subsequently faint yellow solid is poured in beaker, after washing with alcohol 2h ~ 3h, from
The heart, then it is washed with deionized 2h ~ 3h, it is repeated twice, obtains wet metallic organic framework MIL-88A solid；By wet metal
Vacuum drying oven put into by organic backbone MIL-88A solid, is dried 8 ~ 12h at 80 ~ 120 DEG C, obtains described metallic organic framework
MIL-88A。
One the most according to claim 1 utilizes metallic organic framework efficient catalytic activation persulfate or persulfuric acid hydrogen salt
The method processing organic wastewater, it is characterised in that: the PH of described organic wastewater is 2 ~ 9.
One the most according to claim 1 utilizes metallic organic framework efficient catalytic activation persulfate or persulfuric acid hydrogen salt
The method processing organic wastewater, it is characterised in that: in described organic wastewater, add metallic organic framework MIL-88A and mistake in the lump
Sulfate or persulfuric acid hydrogen salt, under normal temperature condition, react in rotating speed is 50 ~ 500 rpm shaking tables, and the response time is 30
~150min。
One the most according to claim 5 utilizes metallic organic framework efficient catalytic activation persulfate or persulfuric acid hydrogen salt
The method processing organic wastewater, it is characterised in that: described persulfate includes in sodium peroxydisulfate, potassium peroxydisulfate and Ammonium persulfate.
More than one.
One the most according to claim 5 utilizes metallic organic framework efficient catalytic activation persulfate or persulfuric acid hydrogen salt
The method processing organic wastewater, it is characterised in that: described persulfuric acid hydrogen salt includes potassium hydrogen persulfate, hydrogen persulfate sodium and over cure
Acid hydrogen ammonium in more than one.
One the most according to claim 5 utilizes metallic organic framework efficient catalytic activation persulfate or persulfuric acid hydrogen salt
The method processing organic wastewater, it is characterised in that: the persulfate added in organic wastewater or persulfuric acid hydrogen salt and organic waste
The mol ratio of the organic pollution in water is 20:1 ~ 100:1.
One the most according to claim 5 utilizes metallic organic framework efficient catalytic activation persulfate or persulfuric acid hydrogen salt
The method processing organic wastewater, it is characterised in that: the dosage of described metallic organic framework MIL-88A is 0.05 ~ 0.6 g/L.
One the most according to claim 5 utilizes metallic organic framework efficient catalytic activation persulfate or hydrogen persulfate
The method of salt treatment organic wastewater, it is characterised in that: described metallic organic framework MIL-88A, through recycled for multiple times, embodies
The catalytic capability that metallic organic framework MIL-88A is maximum.
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