CN105198047A - Electrochemical hydrogenation treatment method of fluoroarene-contaminated wastewater - Google Patents
Electrochemical hydrogenation treatment method of fluoroarene-contaminated wastewater Download PDFInfo
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- CN105198047A CN105198047A CN201510702974.9A CN201510702974A CN105198047A CN 105198047 A CN105198047 A CN 105198047A CN 201510702974 A CN201510702974 A CN 201510702974A CN 105198047 A CN105198047 A CN 105198047A
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- aromatic hydrocarbon
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Abstract
The invention discloses an electrochemical hydrogenation treatment method of fluoroarene-contaminated wastewater. The method comprises the following steps: a supporting electrolyte is added into fluoroarene-contaminated wastewater so as to obtain a catholyte; an electrolytic reaction is carried out in a diaphragm electrolytic cell with a rhodium-modified conducting material used as cathode and a chemically inert conducting material used as anode, and during the electrolytic process, pH of the catholyte is controlled to 1-6, temperature is controlled to 0-50 DEG C and electric current density is controlled to 0.1-10 A/dm<2>; and after the electrolytic reaction, a fluoro-substituting group and aromatic ring in the fluoroarene are completely hydrogenated. The reaction can be carried out in a water system at normal pressure and temperature without an organic solvent. A high concentration (1-50mmol/L) of fluoroarene-contaminated wastewater can be highly efficiently treated at high electric current density (1-5A/dm<2>), and total conversion of fluoroarene is realized. Complete hydrogenation rate of the fluoro-substituting group and aromatic ring is greater than 95%, and yield of fluorinion is greater than 95%.
Description
(1) technical field
The present invention relates to the Electrochemical hydriding treatment process of fluorinated aromatic hydrocarbon pollutant effluents, be specifically related to the electrochemistry complete method for hydrogenation of fluorine in wastewater for aromatic hydrocarbons pollutent fluoro substituents and aromatic ring.
(2) background technology
Fluorinated aromatic hydrocarbon is widely used in modern, medicine manufacture as important intermediate and bulk drug.1994, the global output of fluorinated aromatic hydrocarbon was 10,000 tons; 2000, the output in its whole world then rose to 3.5 ten thousand tons; 2013, the whole world agricultural chemicals of 30 ~ 40% and the medicine of 25% were organic fluorocompound, and the 5 kinds of best medicine wherein sold have 3 kinds to be organic fluorocompound.Fluorinated aromatic hydrocarbon output increases fast and derives from the optimization of its fluorine atom to molecule performance, and it generally has better stability and bioavailability.
Due to fluorinated aromatic hydrocarbon in the world output increase rapidly and its stability at physical environment, it becomes potential environmental pollutant.Due to the high stability of fluorinated aromatic hydrocarbon, often efficiency is very low for the bioremediation that its waste water polluted is conventional and high-level oxidation technology process.Therefore, the method developing efficient degradation fluorinated aromatic hydrocarbon pollutent is necessary very much.At present, multiple oxidation technology has been proved to be fluorinated aromatic hydrocarbon of effectively degrading, these oxidation style comprise the hydrogen peroxide oxidation method [J.Am.Chem.Soc.2013 of two iron-phthalocyanine dyestuff catalysis, 261 (15), 463-469], chlorine peroxidase catalyses oxidation style [Biotechnol.Lett.2007,29:45 – 49], optically catalytic TiO 2 oxidation style [Chem.Eng.J.2007,128,51 – 57] and electrochemical oxidation process [J.Phys.Chem.C2011,115,3888 – 3898].Although fluorinated aromatic hydrocarbon can be oxidized to carbonic acid gas and fluorion by these oxidation style, there is reaction preference difference and the risk that high toxicity fails to understand intermediate product and the fluorine-containing product of high stability may be produced.
Compare with oxidation style, have can realize complete defluorinate and the high advantage of reaction preference although hydrogen reduction can not realize thorough mineralising.The biodegradability of the product of complete hydrogenation defluorinate will greatly improve, and it can be used as industrial chemicals and reclaims, also thoroughly can degrade by routine biochemistry treatment process.The complete hydrogenation defluorination method of fluorinated aromatic hydrocarbon of high chemo-selective has: with solubility ruthenium palladium bimetal complex [Na.Commun.2013,4,1-7] or carbon carry platinum [Adv.Synth.Catal.2012,354,777-782] the carbon-fluorine bond of shortening method optionally on hydrogenation fluorinated aromatic hydrocarbon make it to generate fluorion and floride-free aromatic hydrocarbons; The photochemical catalysis hydride process [GreenChem., 2009,11,942 – 945] of phenyl cationic catalysts optionally hydrogenation defluorinate containing single fluorine aromatic hydrocarbons of electron donating group; NaBH
4the carbon-fluorine bond of electrochemical reducing [TetrahedronLett., 2015,56,1520-1523] the energy selective hydration fluorinated aromatic hydrocarbon promoted makes it to generate floride-free aromatic hydrocarbons.Regrettably, these methods need comparatively harsh reaction conditions (such as use toxic organic solvents or need High Temperature High Pressure etc.), are therefore not suitable as the actual treatment of fluorinated aromatic hydrocarbon pollutant effluents.
For the various deficiencies of above-mentioned various method, McNeill ' s seminar develops catalytic hydrogenation method [Environ.Sci.Technol.2012,46, the 10199-10205 that aluminium dioxide carries rhodium; Environ.Sci.Technol.2013,47,6545-6553], the method can realize the complete hydrogenation of fluorobenzene fluoro substituents and phenyl ring at normal temperatures and pressures with in water medium.The main drawback of the method is, needs to pass into a large amount of hydrogen in reaction process, when processing lower concentration fluorinated aromatic hydrocarbon pollutant effluents, has very high hidden peril of explosion.
(3) summary of the invention
The object of the invention is to provide a kind of Electrochemical hydriding treatment process of fluorinated aromatic hydrocarbon pollutant effluents.In the waste water that fluorinated aromatic hydrocarbon pollutes, add a small amount of ionogen as catholyte, be negative electrode at the electro-conductive material modified with rhodium, in the diaphragm sell being anode with unreactiveness electro-conductive material, anticathode liquid carries out electrolytic reaction.Fluorine in wastewater can be realized can biochemical raising and toxicity reducing of waste water by complete hydrogenation for the fluoro substituents of aromatic hydrocarbons pollutent and aromatic ring; If necessary, also can be reclaimed as industrial chemicals with traditional method (absorption, extraction etc.) by complete all hydrogenated compound in waste water.The present invention can not only solve that existing fluorine in wastewater is poor for aromatic hydrocarbons Pollutant Treatment technology reaction preference, severe reaction conditions and use the problems such as explosive hydrogen in a large number, and can high current density (1 ~ 5A/dm
2), process high density (1 ~ 50mmol/L) fluorinated aromatic hydrocarbon waste water expeditiously.
The technical solution used in the present invention is:
The invention provides a kind of Electrochemical hydriding treatment process of fluorinated aromatic hydrocarbon pollutant effluents, described method for: shown in formula (I) fluorinated aromatic hydrocarbon pollute waste water in, add supporting electrolyte and obtain electrolysis cathode liquid; Be negative electrode at the electro-conductive material modified with rhodium, carry out electrolytic reaction in the diaphragm sell that is anode with unreactiveness electro-conductive material, in electrolytic process, electrolysis cathode liquid pH controls is 1 ~ 6, and temperature is 0 ~ 50 DEG C, and current density is 0.1 ~ 10A/dm
2; After electrolytic reaction terminates, obtain the catholyte containing compound shown in formula (II), realize the complete hydrogenation of fluoro substituents and aromatic ring in fluorinated aromatic hydrocarbon shown in formula (I); Compound shown in described catholyte Chinese style (II) can use traditional method (as absorption, extraction etc.) to reclaim as industrial chemicals, also can directly carry out degradation treatment with routine biochemistry treatment process anticathode liquid;
In formula (I), R is C or N; X is H, CH
3, OH, OCH
3, OCH
2cOOH, NH
2, F, CF
3, CN, COOH, n is one of positive integer between 1 ~ 5;
R and X cotype (I) in formula (II).
Shown in waste water Chinese style (I) of the present invention, the concentration of fluorinated aromatic hydrocarbon is 0.01 ~ 50mmol/L, preferably 1 ~ 50mmol/L.
Further, fluorinated aromatic hydrocarbon pollutent shown in described waste water Chinese style (I) is one of following or the mixing of two kinds and above arbitrary proportion: fluorobenzene, fluorotoluene, fluorophenol, fluorobenzene methyl ether, fluorobenzene fluoroacetic acid, Fluoroaniline, fluorobenzotrifluoride, fluoro benzonitrile, fluorinated acid and fluorinated pyridine.
Electro-conductive material in the electro-conductive material that negative electrode of the present invention is modified with rhodium is one of one of following or conducting polymer modified llowing group of materials: nickel, copper, silver, titanium, graphite, carbon fiber felt or carbon containing conductive plastics.Described conductive polymers is polypyrrole, and described polypyrrole is prepared from through anodic oxidation in 0.5mol/L aqueous sulfuric acid by 0.01 ~ 0.1mol/L pyrrole monomer.The mass loading amount of described rhodium metal is 0.1 ~ 10g/m
2electro-conductive material, is preferably 0.5 ~ 5g/m
2, most preferably 2g/m
2.Described cathode shape is tabular, shaft-like, wire shape, mesh-like, netted, spumescence, ulotrichy or sheet, the mesh-like of preferred development.Negative electrode of the present invention is preferably rhodium modifying foam nickel (2gRh/m
2), rhodium modifying foam copper (2gRh/m
2), rhodium modify expansion silver-colored screen cloth (2gRh/m
2), rhodium modifies titanium net (2gRh/m
2), rhodium modifies containing the graphite cake (2gRh/m of polypyrrole
2), rhodium modifies carbon containing conductive plastic plate (2gRh/m
2), rhodium modifies graphite cake (2gRh/m
2), more preferably described negative electrode is the carbon fiber felt (2gRh/m that rhodium is modified
2).
The technique of electro-conductive material of the present invention being modified rhodium is known, and such as nickel, copper, silver-colored isoreactivity metal can modify rhodium with chemical replacement method or electrodip process; Titanium, graphite, carbon fibre material, conductive plastics or the above-mentioned electro-conductive material having modified conductive polymers can modify rhodium with electrodip process.
Further, the concentration of described supporting electrolyte in electrolysis cathode liquid is 1 ~ 100mmol/L, preferred 5mmol/L.
Anode of the present invention is not key factor, can be any unreactiveness electro-conductive material or alloy, as platinum, graphite, conductive plastics etc.Anode also can be made up of the conductive coating be coated on another kind of material, such as: be applied on titanium metal by the metal oxide containing precious metals of such as ruthenium oxide and so on.The shape of described anode can be the form of tabular, shaft-like, wire shape, mesh-like, netted, spumescence, ulotrichy or sheet, the mesh-like of preferred development.Most preferably described anode is titanium platinum plating net.
Electrolytic reaction of the present invention intermittently can be carried out or carries out with continuous or semi continuous mode.Electrolyzer can be the flow cell channel of steel basin containing electrode or any traditional design.Electrolyzer is diaphragm sell.Available diaphragm material has various negatively charged ion or cationic exchange membrane, the Teflon of porous, asbestos or glass, and preferred perfluorinated sulfonic acid cationic membrane is as the barrier film of electrolyzer.
Although preferably release oxygen as anodic reaction; but also can use other anodic reactions many, comprise the releasing of chlorine molecule and molecular bromine or produce carbonic acid gas by the oxidation of the protective substance of such as formate or oxalate and so on or form valuable by product by the oxidation of organic reactant.Can be such as anolyte of the present invention with 1mol/L sulfuric acid or aqueous hydrochloric acid; Also can be anolyte of the present invention with 1mol/L aqueous sodium hydroxide solution.
In electrolytic reaction process of the present invention, current density changes according to the change in concentration of fluorinated aromatic hydrocarbon in catholyte, and the electrolysis cathode current density be usually applicable to is 0.1 ~ 10A/dm
2, preferably 1 ~ 5A/dm
2.Electrolytic reaction liquid of the present invention pH in reaction process controls 1 ~ 6, and preferably 2.5 ~ 3.5; Temperature is not key factor, but considers that control is convenient, and the temperature be applicable to is 0 ~ 50 DEG C, preferably 20 ~ 30 DEG C.
The present invention carries out required electrolytic reduction by the generally well-known technology in this area.Usually, in the waste water polluted there being fluorinated aromatic hydrocarbon, add a certain amount of supporting electrolyte and pH adjusting agent as catholyte, be negative electrode at the electro-conductive material modified with rhodium, pass into enough electric currents, until obtain the reduction of required degree in the diaphragm sell that is anode with unreactiveness electro-conductive material.After electrolytic reaction terminates, traditional technology (as absorption, extraction etc.) can be utilized to reclaim electrolysate in catholyte, or directly process the waste water after electrolysis treatment with traditional biochemical processing method.
Reaction (for fluorophenol) involved in the Electrochemical hydriding treatment process of fluorinated aromatic hydrocarbon pollutant effluents of the present invention:
(1) cathodic reaction:
(2) anodic reaction:
(n+3)H
2O-(2n+6)e
-→(n+3)/2O
2 +(2n+6)H
+
(3) total reaction:
Beneficial effect of the present invention is mainly reflected in: (1) reaction can be carried out in the aqueous systems of normal temperature and pressure and organic solvent-free; (2) high volatile hydrogen is not used in reaction process; (3) fluorine in wastewater is for the fluoro substituents of aromatic hydrocarbons pollutent and the alternative hydrogenation completely of aromatic ring, and this greatly can improve the biodegradability of waste water and reduce the toxicity of waste water; (4) can high current density (1 ~ 5A/dm
2), process high density (1 ~ 50mmol/L) fluorinated aromatic hydrocarbon waste water expeditiously, realize the conversion completely of fluorinated aromatic hydrocarbon, fluoro substituents and the complete hydrogenation ratio of aromatic ring are greater than 95%, and fluorion yield is greater than 95%.
(4) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
The preparation method of cathode material described in the embodiment of the present invention is with reference to [Colloid.Surf.B:Biointerfaces2014,261,121,444-450; AnalyticaChimicaActa2009,632,63-68].
The Electrochemical hydriding process of embodiment 1 p-fluorophenol pollutant effluents
Using the aqueous solution 1000mL of 5mmoL/L p-fluorophenol+5mmol/L sodium sulfate+5mmol/L sodium-chlor as catholyte; 1mol/L aqueous sulfuric acid is as anolyte.Carbon fiber felt (the 2gRh/m that rhodium is modified
2) as negative electrode, titanium platinum plating net is anode, barrier film sheet frame groove is electrolysis reactor, and perfluoro sulfonic acid membrane is barrier film.
In electrolytic process, it is 20 ~ 25 DEG C that temperature controls, and current density controls as 3A/dm
2, catholyte pH controls 2.5 ~ 3.5.Electrolysis is stopped after passing into 8F/mol4-fluorophenol electricity.After electrolysis terminates, catholyte (30mL) is transferred in shunting funnel, divides three anticathode liquid to extract with 30mL methylene dichloride; Extraction terminates rear merging three parts of extraction liquids, then by its by a funnel containing 5g anhydrous sodium sulphate solid to remove residual moisture; Finally the laggard promoting the circulation of qi analysis of hplc of 500mL is settled to extraction liquid volumetric flask.Separately get 5mL catholyte deionized water and dilute 20 times, then analyze with chromatography of ions.Gas-chromatography and the display of ion chromatography result: the yield 46% of pimelinketone, the yield of hexalin is 53%, the yield of fluorion is 100%.
Analytical conditions for gas chromatography is: HP-INNOWAX (30mx320 μm of x0.5 μm) is separator column; Detector is FID; Hydrogen flowing quantity is 30mL/min; Post case temperature is 75-230 DEG C; Heat-up rate is 15 DEG C/min.
Chromatography of ions condition: IonPacAS19 anion-exchange column (4 × 250mm) is separator column; Gradient program is: 0 → 5min (10mMKOH), 5 → 20Min (10 → 40mMKOH); Flow velocity is: 1mL/Min; INSTRUMENT MODEL is: DionexICS-2000).
The Electrochemical hydriding process of embodiment 2 ~ embodiment 29 different fluorinated aromatic hydrocarbon pollutant effluents
Embodiment 2 ~ embodiment 29 is carried out according to the experiment parameter of table 1, and all the other operations are with embodiment 1.
Table 1 embodiment 2 ~ embodiment 29 experiment condition and result
Embodiment 30 ~ embodiment 37 uses different rhodium to modify the Electrochemical hydriding process of p-fluorophenol pollutant effluents of negative electrode
Embodiment 30 ~ embodiment 37 is carried out according to the experiment parameter of table 2, and all the other operations are with embodiment 1.
Table 2 embodiment 30 ~ embodiment 37 experiment condition and result
a
athe anolyte that 1mol/L aqueous sodium hydroxide solution is; Ruthenized titanium net is anode.
Comparative example 1 ~ comparative example 8 uses the Electrochemical hydriding process of p-fluorophenol pollutant effluents of the substrate cathode of not modifying rhodium
Comparative example 1 ~ comparative example 8 is carried out according to the experiment parameter of table 3, and all the other operations are with embodiment 1.
Table 3 comparative example 1 ~ comparative example 8 experiment condition and result
a
athe anolyte that 1mol/L aqueous sodium hydroxide solution is; Ruthenized titanium net is anode.
Claims (10)
1. an Electrochemical hydriding treatment process for fluorinated aromatic hydrocarbon pollutant effluents, it is characterized in that described method for: shown in formula (I) fluorinated aromatic hydrocarbon pollute waste water in, add supporting electrolyte and obtain electrolysis cathode liquid; Be negative electrode at the electro-conductive material modified with rhodium, carry out electrolytic reaction in the diaphragm sell that is anode with unreactiveness electro-conductive material, in electrolytic process, electrolysis cathode liquid pH controls is 1 ~ 6, and temperature is 0 ~ 50 DEG C, and current density is 0.1 ~ 10A/dm
2; After electrolytic reaction terminates, obtain the catholyte containing compound shown in formula (II), realize the complete hydrogenation of fluoro substituents and aromatic ring in fluorinated aromatic hydrocarbon shown in formula (I); Described supporting electrolyte is one of following or the mixing of two kinds of arbitrary proportions: sodium sulfate, sodium-chlor;
In formula (I), R is C or N; X is H, CH
3, OH, OCH
3, OCH
2cOOH, NH
2, F, CF
3, CN, COOH, n is one of positive integer between 1 ~ 5;
R and X cotype (I) in formula (II).
2. the Electrochemical hydriding treatment process of fluorinated aromatic hydrocarbon pollutant effluents as claimed in claim 1, is characterized in that the concentration of fluorinated aromatic hydrocarbon shown in described waste water Chinese style (I) is 1 ~ 50mmol/L.
3. the Electrochemical hydriding treatment process of fluorinated aromatic hydrocarbon pollutant effluents as claimed in claim 1, is characterized in that fluorinated aromatic hydrocarbon shown in described waste water Chinese style (I) is one of following or the mixing of two kinds and above arbitrary proportion: fluorobenzene, fluorotoluene, fluorophenol, fluorobenzene methyl ether, fluorobenzene fluoroacetic acid, Fluoroaniline, fluorobenzotrifluoride, fluoro benzonitrile, fluorinated acid and fluorinated pyridine.
4. the Electrochemical hydriding treatment process of fluorinated aromatic hydrocarbon pollutant effluents as claimed in claim 1, is characterized in that electro-conductive material in the electro-conductive material that described negative electrode is modified with rhodium is one of one of following or conducting polymer modified llowing group of materials: nickel, copper, silver, titanium, graphite, carbon fiber felt or carbon containing conductive plastics.
5. the Electrochemical hydriding treatment process of fluorinated aromatic hydrocarbon pollutant effluents as claimed in claim 1, is characterized in that the mass loading amount of rhodium in described negative electrode is 0.1 ~ 10g/m
2electro-conductive material.
6. the Electrochemical hydriding treatment process of fluorinated aromatic hydrocarbon pollutant effluents as claimed in claim 1, is characterized in that described negative electrode is one of following: the carbon containing conductive plastic plate that carbon fiber felt, rhodium that graphite cake, rhodium that titanium net, rhodium that expansion silver screen cloth, rhodium that foam copper, rhodium that nickel foam, rhodium that rhodium is modified are modified are modified are modified are modified are modified are modified or the graphite cake containing polypyrrole that rhodium is modified.
7. the Electrochemical hydriding treatment process of fluorinated aromatic hydrocarbon pollutant effluents as claimed in claim 1, is characterized in that the concentration of described supporting electrolyte in electrolysis cathode liquid is 1 ~ 100mmol/L.
8. the Electrochemical hydriding treatment process of fluorinated aromatic hydrocarbon pollutant effluents as claimed in claim 1, it is characterized in that in described electrolytic process that electrolysis cathode liquid pH controls is 2.5 ~ 3.5, and temperature is 20 ~ 30 DEG C, and current density is 1 ~ 5A/dm
2.
9. the Electrochemical hydriding treatment process of fluorinated aromatic hydrocarbon pollutant effluents as claimed in claim 1, is characterized in that described anode is titanium platinum plating net.
10. the Electrochemical hydriding treatment process of fluorinated aromatic hydrocarbon pollutant effluents as claimed in claim 1, is characterized in that described diaphragm sell septation is perfluorinated sulfonic acid cationic membrane.
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|---|---|---|---|---|
| CN115135613A (en) * | 2020-02-21 | 2022-09-30 | 西门子能源美国公司 | Fluorocarbon destruction systems and methods |
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| JP2007229565A (en) * | 2006-02-28 | 2007-09-13 | Ebara Corp | Treatment apparatus and treatment method of hardly biodegradable substance content organic wastewater |
| CN204198463U (en) * | 2014-09-11 | 2015-03-11 | 北京今大禹环保技术有限公司 | A kind of continuum micromeehanics formula solid state electrolyte electric tank cathode system |
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| 李美丽: "电化学条件下含氟芳香化合物脱氟氢化反应的研究", 《中国优秀硕士学位论文全文数据库（电子期刊）-工程科技I辑》 * |
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| CN115135613A (en) * | 2020-02-21 | 2022-09-30 | 西门子能源美国公司 | Fluorocarbon destruction systems and methods |
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Effective date of registration: 20201127 Address after: 256600, Shandong City, Binzhou Province foreshore City north of the new wing Yong Road South Patentee after: Shoujian Technology Co.,Ltd. Address before: 310014 Hangzhou city in the lower reaches of the city of Zhejiang Wang Road, No. 18 Patentee before: ZHEJIANG University OF TECHNOLOGY |