CN105288929B - With Keggin-type heteropoly compound H3PW12O40Homogeneous catalysis technique for catalyst degradation organic pollution deca-BDE - Google Patents
With Keggin-type heteropoly compound H3PW12O40Homogeneous catalysis technique for catalyst degradation organic pollution deca-BDE Download PDFInfo
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Abstract
The present invention is one kind with Keggin-type heteropoly compound H3PW12O40For the homogeneous catalysis technique of catalyst degradation organic pollution deca-BDE, its main feature is that, including Keggin-type Heterocompound catalyst H3PW12O40Synthesis, Keggin-type Heterocompound catalyst H3PW12O40Characterization, to the analysis of the homogeneous catalysis of organic pollution deca-BDE and homogeneous catalysis degradation effect and catabolite, it is scientific and reasonable with technological process, process equipment is simple, degradation efficiency is high, less energy consumption, the advantages that catalyst comprehensive utilization ratio is high, and environment protecting is good solves the problems, such as that environmental area removes organic pollution deca-BDE.
Description
Technical field
The invention belongs to environmental catalysis field more particularly to Keggin-type heteropoly compound H3PW12O40It is dropped for catalyst
Solve the homogeneous catalysis technique of organic pollution deca-BDE.
Background technology
Polybrominated diphenyl ethers (PBDEs) has been widely used in as efficient flame-retarding agent in plastic products, because it has the whole world
The widely distributed and good bioconcentration of property cause environment in terms of highest attention.At present in certain deposits, ocean
The presence of PBDEs is detected in biology, food samples, human blood and tissue.It is reported that PBDEs can influence the work of enzyme
Property and as incretion interferent, nervous system is damaged in the critical period of brain development.For typical commercial
PBDEs products (such as five, eight and decabromodiphenyl oxide), the demand to decabromodiphenyl oxide (BDE209) is the largest, about the world
In the range of PBDEs use total amount 75%.In the deposit in the Delta of the Pearl River and South China Sea region, the concentration area of BDE209
Between for 0.4-7340ng/g, account for about the 72.6-99.7% of PBDEs total amounts, therefore, BDE209 pollutions can be eliminated by finding one
Method is most important.In recent years, researchers have also paid great effort in this regard, by carrying out photodissociation to BDE209, going back
Original degradation, hydrothermal technique and biological approach using Anaerobic culturel etc..Although these methods may finally remove BDE209, speed
Degree is very slow, takes long, and during degradation, because BDE209 has stronger hydrophobicity and stability, thus is
Between product acquisition and analysis bring difficulty；On the other hand, these reactions may bring some negative effects to environment, degradation
The homologue of the low bromo generated has higher toxicity compared to BDE209.
Since the last few years, the Chemical self-assembly of polyacid, the surface chemistry of polyacid, polyacid catalytic chemistry, it is particularly more
Research that acid is catalyzed organic compound selective oxidation and the theoretical chemistry of polyacid etc. become the several of Chemistry of Polyacids area research
A important hot issue.Polyacid compound has determining structure, its soda acid and redox property can be by changing its change
It learns composition and is adjusted in very large range；Polyacid compound dissolubility is good, can readily be dissolved in polar solvent, and
And in solid-state, polyacid compound has good thermal stability；Polyacid compound has acid and oxidation-reduction quality simultaneously, and
It can be carried out quick reversible oxidation-reduction reaction under mild conditions；Polyacid compound has unique coordination ability,
Reaction intermediate can be stablized.In most polyacid compounds, structure with Keggin is most stable and is readily available, and has both
Good stability and oxidation-reduction quality can make homogeneous or heterogeneous reaction, and environmentally safe, which is analyzing
The fields such as chemistry, medicine, material science have potential application prospect, the polyacid compound of this class formation and its certain derivatives
Object shows high catalytic activity in some catalytic process.If Keggin-type heteropoly compound H can be utilized3PW12O40
The advantages of go solve BDE209 caused by pollution problem be that those skilled in the art thirst for solving always, but not yet solve so far
Problem certainly.
Invention content
The object of the present invention is to carry out substantial improvements and innovation to the prior art, provide a kind of catalyst utilization it is high,
Low energy consumption, free of contamination with Keggin heteropoly compounds H3PW12O40For the equal of catalyst degradation organic pollution deca-BDE
Phase Catalytic processes.
Realize the object of the invention the technical solution adopted is that, one kind with Keggin-type heteropoly compound H3PW12O40For catalysis
The homogeneous catalysis technique of agent degradable organic pollutant deca-BDE, it is characterized in that, it includes the following steps：
(1) Keggin-type Heterocompound catalyst H3PW12O40Synthesis
Sodium tungstate 99.95g, disodium hydrogen phosphate 32.23g with boiling water 150mL are mixed, the concentrated sulfuric acid is added dropwise under magnetic stirring
80mL obtains the solution with pale yellow precipitate, and solution is cooled to room temperature, and adds in ether 60mL extractions, the lower floor after extraction
Yellow heteropoly acid etherate purges to obtain the solids of yellow by air stream, in 70 DEG C of drying of vacuum drying chamber, 7-8h
Obtain Keggin-type Heterocompound catalyst H3PW12O40；
(2) Keggin-type Heterocompound catalyst H3PW12O40Characterization
Product after synthesis is characterized：Take the Keggin-type Heterocompound catalyst H of 1mg3PW12O40With 10mg
With the infrared spectrum of fourier infrared spectrophotometer test catalyst, the catalyst after synthesis is matched for specpure KBr tablettings
Into a concentration of 2 × 10-5The solution of mol/L is placed in the quartz colorimetric utensil of 10 × 10mm, under anaerobic, with UV, visible light point
Light photometer tests the ultraviolet-visible absorption spectroscopy of catalyst, is repeated by the infrared spectrum and ultraviolet-visible absorption spectroscopy
Three times；
(3) to the homogeneous catalysis of organic pollution deca-BDE
In synthesis H3PW12O40During, the solution after the addition concentrated sulfuric acid is placed in three mouthfuls of glass reaction bottles, to
1mg deca-BDEs are added in reaction bulb, open magnetic stirring apparatus, O2Aeration starts to react, and entire reaction process is in camera bellows
It completes, in degradation process, 2mL is sampled every 10min, 15min is centrifuged with the rotating speed of 4000rpm with centrifuge, after centrifugation
Supernatant directly carries out the analysis of next stage by the membrane filtration of 0.22um；
(4) analysis of homogeneous catalysis degradation effect and catabolite
During homogeneous catalysis, the concentration and midbody product of deca-BDE in order to obtain, will at interval of
The supernatant that 10min is collected into passes through high performance liquid chromatography and ion chromatography；Instrument pair is used in conjunction by gas chromatography-mass spectrum again
The catabolite of homogeneous catalysis carries out qualitative and quantitative analysis, in the homogeneous catalytic reaction to organic pollution deca-BDE
When carrying out 14 hours, deca-BDE is completely removed.
Advantages of the present invention is embodied in：
(1) it by the analysis of high performance liquid chromatography and ion chromatography to supernatant, studies the concentration of BDE209, generate
Br-Concentration vs. time response, obtain reaction carry out 14 hours after, the deca-BDE (BDE209) of addition is removed completely
It goes；With bromide ion (Br-) the increase of concentration show the generations of some brominated intermediates, be used in conjunction using gas chromatography-mass spectrum
Instrument it is qualitative and quantitative analyze catabolite, by extending the time, replacing oxidant (H2O2、KHSO5) method can remove
Remove the intermediate of the low bromo generated；
(2) technological process is scientific and reasonable, and process equipment is simple, and degradation efficiency is high, less energy consumption, catalyst comprehensive utilization ratio
Height, environment protecting is good, solves the problems, such as that environmental area removes organic pollution deca-BDE.
Description of the drawings
Fig. 1 is the Keggin-type Heterocompound catalyst H synthesized in the present invention3PW12O40Fourier infrared spectrum show
It is intended to；
Fig. 2 is the Keggin-type Heterocompound catalyst H synthesized in the present invention3PW12O40Ultraviolet-visible absorption spectroscopy
Schematic diagram；
Fig. 3 is by the analysis of high performance liquid chromatography and ion chromatography to supernatant, the concentration of obtained BDE209 and production
Raw Br-Concentration vs. time response curve schematic diagram.
Specific embodiment
With reference to Fig. 1-3, one kind of the invention is with Keggin-type heteropoly compound H3PW12O40For catalyst degradation organic contamination
The homogeneous catalysis technique of object deca-BDE, includes the following steps：
(1) Keggin-type Heterocompound catalyst H3PW12O40Synthesis
Sodium tungstate 99.95g, disodium hydrogen phosphate 32.23g with boiling water 150mL are mixed, the concentrated sulfuric acid is added dropwise under magnetic stirring
80mL obtains the solution with pale yellow precipitate, and solution is cooled to room temperature, and adds in ether 60mL extractions, the lower floor after extraction
Yellow heteropoly acid etherate purges to obtain the solids of yellow by air stream, in 70 DEG C of drying of vacuum drying chamber, 7-8h
Obtain Keggin-type Heterocompound catalyst H3PW12O40；Fig. 1 is the Keggin-type heteropoly compound catalysis synthesized in the present invention
Agent H3PW12O40FTIR spectrum schematic diagram, in the diagram wave number be 802cm-1、890cm-1、987cm-1With
1080cm-1Four characteristic peaks confirm this research synthesis compound be Keggin-type heteropoly compound H3PW12O40；Fig. 2
It is the Keggin-type Heterocompound catalyst H synthesized in the present invention3PW12O40Ultraviolet-visible absorption spectroscopy schematic diagram, showing
The characteristic absorption peak for being intended to a length of 212nm and 263nm of medium wave demonstrates again that the compound of the present embodiment synthesis is miscellaneous for Keggin-type
More compound H3PW12O40；
(2) Keggin-type Heterocompound catalyst H3PW12O40Characterization
Product after synthesis is characterized：Take the Keggin-type Heterocompound catalyst H of 1mg3PW12O40With 10mg
With the infrared spectrum of fourier infrared spectrophotometer test catalyst, the catalyst after synthesis is matched for specpure KBr tablettings
Into a concentration of 2 × 10-5The solution of mol/L is placed in the quartz colorimetric utensil of 10 × 10mm, under anaerobic, with UV, visible light point
Light photometer tests the ultraviolet-visible absorption spectroscopy of catalyst, is repeated by the infrared spectrum and ultraviolet-visible absorption spectroscopy
Three times；
(3) to the homogeneous catalysis of organic pollution deca-BDE
In synthesis H3PW12O40During, the solution after the addition concentrated sulfuric acid is placed in three mouthfuls of glass reaction bottles, to
1mg deca-BDEs are added in reaction bulb, open magnetic stirring apparatus, O2Aeration starts to react, and entire reaction process is in camera bellows
It completes, in degradation process, 2mL is sampled every 10min, 15min is centrifuged with the rotating speed of 4000rpm with centrifuge, after centrifugation
Supernatant directly carries out the analysis of next stage by the membrane filtration of 0.22um；
(4) analysis of homogeneous catalysis degradation effect and catabolite
With reference to Fig. 3, during homogeneous catalysis, the concentration and midbody product of deca-BDE in order to obtain will be
Pass through high performance liquid chromatography and ion chromatography at interval of the supernatant that 10min is collected into；Connected again by gas chromatography-mass spectrum
Qualitative and quantitative analysis is carried out to the catabolite of homogeneous catalysis with instrument, is urged to the homogeneous of organic pollution deca-BDE
When change reaction carries out 14 hours, deca-BDE is completely removed.
The particular embodiment of the present invention has made present disclosure detailed explanation, but does not limit to the present embodiment,
Those skilled in the art are according to the present invention to enlighten any obvious change done, and belongs to rights protection of the present invention
Range.
Claims (1)
1. one kind is with Keggin-type heteropoly compound H3PW12O40Homogeneous for catalyst degradation organic pollution deca-BDE is urged
Chemical industry skill, it is characterized in that, it includes the following steps：
(1) Keggin-type Heterocompound catalyst H3PW12O40Synthesis
Sodium tungstate 99.95g, disodium hydrogen phosphate 32.23g with boiling water 150mL are mixed, concentrated sulfuric acid 80mL is added dropwise under magnetic stirring
The solution with pale yellow precipitate is obtained, solution is cooled to room temperature, adds in ether 60mL extractions, lower floor's yellow after extraction is miscellaneous
Polyacid etherate purges to obtain the solids of yellow by air stream, and in 70 DEG C of drying of vacuum drying chamber, 7-8h is obtained
Keggin-type Heterocompound catalyst H3PW12O40；
(2) Keggin-type Heterocompound catalyst H3PW12O40Characterization
Product after synthesis is characterized：Take the Keggin-type Heterocompound catalyst H of 1mg3PW12O40With 10mg spectroscopic pure
KBr tablettings, with fourier infrared spectrophotometer test catalyst infrared spectrum, the catalyst after synthesis is made into concentration
It is 2 × 10-5The solution of mol/L is placed in the quartz colorimetric utensil of 10 × 10mm, under anaerobic, with UV, visible light spectrophotometric
The ultraviolet-visible absorption spectroscopy of measurement examination catalyst, by the infrared spectrum and ultraviolet-visible absorption spectroscopy in triplicate；
(3) to the homogeneous catalysis of organic pollution deca-BDE
In synthesis H3PW12O40During, the solution after the addition concentrated sulfuric acid is placed in three mouthfuls of glass reaction bottles, to reaction
1mg deca-BDEs are added in bottle, open magnetic stirring apparatus, O2Aeration starts to react, and entire reaction process is completed in camera bellows,
In degradation process, 2mL is sampled every 10min, 15min is centrifuged with the rotating speed of 4000rpm with centrifuge, by the supernatant after centrifugation
By the membrane filtration of 0.22um, the analysis of next stage is directly carried out；
(4) analysis of homogeneous catalysis degradation effect and catabolite
During homogeneous catalysis, the concentration and midbody product of deca-BDE, will receive at interval of 10min in order to obtain
The supernatant collected passes through high performance liquid chromatography and ion chromatography；Instrument is used in conjunction to homogeneously urging by gas chromatography-mass spectrum again
The catabolite of change carries out qualitative and quantitative analysis, and 14 are carried out in the homogeneous catalytic reaction to organic pollution deca-BDE
During hour, deca-BDE is completely removed.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1923318A (en) * | 2006-09-07 | 2007-03-07 | 复旦大学 | Removing method for decabromodiphenyl ether causing environmental pollution |
| CN101816828A (en) * | 2010-04-23 | 2010-09-01 | 华南理工大学 | Method for rapidly degrading decabromodiphenyl oxide in organic series by nano Pd/C catalyst |
| CN102658119A (en) * | 2012-04-11 | 2012-09-12 | 大连交通大学 | Novel polyoxometallate compound, preparation method thereof and application thereof |
| CN103240076A (en) * | 2013-05-12 | 2013-08-14 | 大连理工大学 | Method for preparing supported molybdenum-oxide-based and tungsten-oxide-based oxidation desulfurization catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6723349B1 (en) * | 1999-10-12 | 2004-04-20 | Emory University | Polyoxometalate materials, metal-containing materials, and methods of use thereof |
| AU2003263735A1 (en) * | 2002-05-03 | 2003-11-11 | Emory University | Materials for degrading contaminants |
| US9126185B2 (en) * | 2011-09-30 | 2015-09-08 | The United States Of America, As Represented By The Secretary Of The Navy | Porous polymer supported polyoxometalates |
| GB201308178D0 (en) * | 2013-05-07 | 2013-06-12 | Acal Energy Ltd | Redox systems |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1923318A (en) * | 2006-09-07 | 2007-03-07 | 复旦大学 | Removing method for decabromodiphenyl ether causing environmental pollution |
| CN101816828A (en) * | 2010-04-23 | 2010-09-01 | 华南理工大学 | Method for rapidly degrading decabromodiphenyl oxide in organic series by nano Pd/C catalyst |
| CN102658119A (en) * | 2012-04-11 | 2012-09-12 | 大连交通大学 | Novel polyoxometallate compound, preparation method thereof and application thereof |
| CN103240076A (en) * | 2013-05-12 | 2013-08-14 | 大连理工大学 | Method for preparing supported molybdenum-oxide-based and tungsten-oxide-based oxidation desulfurization catalysts |
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