CN101302051B - Graphite electrode for electrochemical treatment of phenolic waste water - Google Patents
Graphite electrode for electrochemical treatment of phenolic waste water Download PDFInfo
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- CN101302051B CN101302051B CN2008100187455A CN200810018745A CN101302051B CN 101302051 B CN101302051 B CN 101302051B CN 2008100187455 A CN2008100187455 A CN 2008100187455A CN 200810018745 A CN200810018745 A CN 200810018745A CN 101302051 B CN101302051 B CN 101302051B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 76
- 239000010439 graphite Substances 0.000 title claims abstract description 76
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002351 wastewater Substances 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 230000004913 activation Effects 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 239000004593 Epoxy Substances 0.000 claims description 28
- 238000005868 electrolysis reaction Methods 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 19
- 239000008151 electrolyte solution Substances 0.000 claims description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 16
- 238000012545 processing Methods 0.000 abstract description 11
- 239000013067 intermediate product Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002848 electrochemical method Methods 0.000 abstract 1
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 239000003822 epoxy resin Substances 0.000 abstract 1
- 229920000647 polyepoxide Polymers 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 238000000748 compression moulding Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 150000004054 benzoquinones Chemical class 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000009825 accumulation Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- -1 halo phenols Chemical class 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000010815 organic waste Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000009284 supercritical water oxidation Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 1
- HXKWSTRRCHTUEC-UHFFFAOYSA-N 2,4-Dichlorophenoxyaceticacid Chemical compound OC(=O)C(Cl)OC1=CC=C(Cl)C=C1 HXKWSTRRCHTUEC-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 229960001138 acetylsalicylic acid Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- KSSNXJHPEFVKHY-UHFFFAOYSA-N phenol;hydrate Chemical compound O.OC1=CC=CC=C1 KSSNXJHPEFVKHY-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 239000003171 wood protecting agent Substances 0.000 description 1
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a graphite electrode for phenolic wastewater electrochemistry treatment. The electrode uses graphite, epoxy resin and firming agent as main raw material and is prepared by the steps of mixing, molding, solidification, roasting, activation and re-roasting, wherein, the activation is electrochemical activation. The graphite electrode has high electrochemical activation for phenol in water, shows good removing effect and also has good removing effect on an intermediate product degraded by the phenol. The novel graphite electrode has widespread raw material, low price, simple processing and manufacturing process and the marked effect of phenolic wastewater treatment and can be used as the electrode for treating the phenolic wastewater by an electrochemical method.
Description
Technical field
The invention belongs to the treatment of Organic Wastewater field, be specifically related to a kind of Graphite Electrodes that is used for the phenolic wastewater electrochemical treatment.
Background technology
Modern industrial or agricultural high speed development all has a large amount of organic waste water to produce every day.The organic waste water that is produced then can pollute environment as without handling directly discharging, jeopardizes HUMAN HEALTH.Phenol is a kind of important industrial raw material, all is widely used in all respects of national economy.Phenol can be used for making resol and hexanolactam, also can be used for producing the halo phenols.The chlorinated phenol of gained can be used as raw material and is used to produce 2,4 dichlorophenoxyacetic acid and 2,4, weedicides such as 5-trichlorophenoxyacetic acid, wood preservative, miticide, leather preservative and sterilant etc.Phenol also can be used for preparing alkylphenol and further prepares alkylphenol, formaldehydes polymkeric substance, can be used as oxidation inhibitor, nonionogenic tenside, softening agent, petroleum products additive.Phenol also is the raw material of a lot of medicine (as Whitfield's ointment, acetylsalicylic acid and sulfa drug etc.), synthetic perfume, dyestuff.In addition, the dilute aqueous soln of phenol can directly be used as sanitas and sterilizing agent.
The waste water that contains phenol as not treated and direct discharging meeting works the mischief to aquatic organism, and can influence HUMAN HEALTH by food chain.Phenol becomes one of 129 kinds of priority pollutants that USEPA lists because of its high toxicity, high oxygen requirement (theoretical oxygen demand of every mg phenol is 2.38mg) and difficult for biological degradation, China also classifies phenolic wastewater as needs one of harmful waste water that emphasis solves.Research and develop economical and practical phenol removal method, have very important realistic meaning.Phenol is a kind of thoroughly organism of processing that is difficult to, main treatment process has biological process, coagulant sedimentation, active carbon adsorption, ozone oxidation method, foamet, ion exchange method, reverse osmosis method and ultrafiltration process at present, in these methods, perhaps treatment effect is relatively poor, cost is too high, perhaps there are secondary pollution, subsequent disposal difficulty, cause these methods to be difficult to obtain actual applying.
High-level oxidation technology (AOPs) can effectively be degraded to phenolic wastewater, generally acknowledge that at present the outstanding AOPs of treatment effect has ozone oxidation method, Fenton reagent method, photocatalytic oxidation, supercritical water oxidation method and electrochemical process etc. the ozone generating apparatus current consumption of ozone oxidation is very high, and utilization rate of electrical is very low, though make the higher .Fenton reagent of its processing cost method can remove target contaminant; But the clearance to TOC is low at normal temperatures and pressures; Photocatalytic method is difficult to effectively suppress the compound of light induced electron and hole, and photocatalysis efficiency is very low; Supercritical water oxidation method is high to the material requirements of reactor, seeks ideal and can corrosion-resistant for a long time, high temperature resistant, high voltage bearing reactor material still have any problem, and also has certain distance with widespread use.Electrochemical process has the processing efficiency height, cost is low, instrument is simple, easy and simple to handle, take up an area of and less, easily to realize automatization, advantages of environment protection, having shown its distinctive advantage aspect the processing of bio-refractory waste water, favored gradually.Electrochemical process is handled in the organic waste water, and electrode is a The key factor.Have characteristics such as good conductivity, electrochemical activity height, physicochemical property are stable as the material requirements of electrode.Electrode in the electrochemical process mainly is to adopt some rare noble metals, and gets by a series of modification at present, its cost is higher, complex manufacturing process, and the working face of electrode is actively limited, processing efficiency is difficult to significantly improve, and this is restricted with regard to the application that makes electrochemical process.Therefore, prepare that a kind of treatment effect is good, inexpensive, the electrode of wide material sources, have great significance for the widespread use of electrochemical process.Graphite has good electrical conductivity, and wide material sources, cheap, can be used as the electrode materials that electrochemical process is handled, but common Graphite Electrodes activity is low, to the phenolic wastewater poor processing effect, and the electrode instability, be easy to loss, be difficult to obtain widespread use
Summary of the invention
The objective of the invention is needs according to the phenolic wastewater processing, problem at the electrochemical process existence, a kind of active height of research preparation, good stability, wide material sources, cheap electrode are used electrochemical process widely, and phenolic wastewater is able to effective processing.
Another object of the present invention provides a kind of preparation method of above-mentioned electrode.
Purpose of the present invention can reach by following measure:
A kind of Graphite Electrodes that is used for the phenolic wastewater electrochemical treatment, this electrode is a main raw material with graphite, Resins, epoxy and solidifying agent, through mixing, moulding, curing, baking, activation with dry by the fire step preparation again and get, wherein said activation is an electrochemical activation.
A kind of preparation is used for the method for the Graphite Electrodes of phenolic wastewater electrochemical treatment, is main raw material with graphite, Resins, epoxy and solidifying agent, passes through mixing, moulding, curing, baking, activation and dries by the fire the step preparation again, and wherein said activation is an electrochemical activation.
Wherein Resins, epoxy is 618 Resins, epoxy (blue star novel material resin processing plants), and is also available 616,634 or 637, and its quality is 10～30% of a graphite; Solidifying agent is improvement amine 593 solidifying agent (blue star novel material resin processing plant), other improvement amine curing agents such as also available 590,701, T-31 or T-33, and its quality is 10～30% of a Resins, epoxy; Solvent during mixing is an acetone.
The solidified temperature is 15～35 ℃ (preferred 20～30 ℃), and the time is 8～16h.
The temperature of baking is 130～170 ℃, and the time is 0.5～4h.
When activating, make electrolytic solution, need be fixed on the anode by activated electrode, place and carry out electrolysis between anode and cathode, use acetone drip washing after the electrolysis with sodium acetate, anhydrous, acetone, water and Glacial acetic acid with the electrochemical process counter electrode.Wherein electrolytic solution is acetone, water and the acetum of 0.05～0.15mol/L sodium acetate, anhydrous, and the volume ratio of acetone, water and acetic acid is 55～45: 35～45: 10, and electrochemical activation voltage is 22.0～24.0V.Electrode to be activated and cathode distance are 0.05～1.5cm.
The temperature of multiple baking is 110～140 ℃, and the time is 0.5～4h.
Purpose of the present invention specifically can reach by following measure:
(1) batch mixing: high purity graphite, Resins, epoxy, solidifying agent mix.Promptly take by weighing Resins, epoxy and solidifying agent earlier, add solvent again, stirring makes Resins, epoxy fully dissolve mixing, is poured in the high purity graphite powder, fully stirs, and it is mixed.
(2) compression moulding: the raw material that mixes is packed in the mould into compression moulding.
(3) solidify: the graphite rod after the compression moulding is sloughed mould, puts in the air 20～30 ℃ and places 8～16h down, allows its spontaneous curing.
(4) baking: the graphite rod of gained is put 130～170 ℃ of baking 0.5～4h down behind the forming and hardening.
(5) activation: adopt electrochemical process that the graphite rod electrode of preparation is activated, make anode and negative electrode respectively with common graphite rod, be close to and it fastened on anode the graphite rod of preparation is parallel with anode with cotton thread, make positive terminal equal with graphite rod one end of preparation, the graphite rod of preparation place between the anode and cathode and with negative electrode at a distance of 0.05～1.5cm (preferred 0.5cm), to contain the acetone of 0.05～0.15M sodium acetate, anhydrous: water: Glacial acetic acid=55～45: 35～45: the solution of 10 (V/V/V) is electrolytic solution, with the Glass Containers is electrolyzer, electrolysis voltage is 22.0～24.0V, and used for electrolyte heating in water bath constant temperature is at 25 ± 1 ℃.The electrolysis notch covers to prevent volatilization such as acetone with polyethylene film during electrolysis, only stays electrodes exposed outside, electrolysis place 8～12h.After electrolysis treatment finishes, graphite rod with 60mL acetone with the velocity axis of 0.6～0.8mL/min to drip washing.
(6) multiple baking: after drip washing finishes, graphite rod is placed 110～140 ℃ of baking 0.5～4h, so far, electrode preparation finishes.
Characteristics of the present invention:
(1) electrode of the present invention is a raw material with Graphite Powder 99, Resins, epoxy, solidifying agent and acetone, and wide material sources are cheap.
(2) electrode preparation of the present invention is through batch mixing, and---------thermal treatment---activation---re-heat is handled, and the technology uniqueness makes electrode have good performance in curing in compression moulding.
(3) electrode activation of the present invention adopts electrochemical process, and electrolytic solution adopts sodium acetate, anhydrous, acetone, water, glacial acetic acid solution, makes electrode have high activity.
(4) electrode of the present invention handle phenol when (also can be used for other phenols) as phenolic compounds such as nitrophenol, chlorophenol or dihydroxy-benzenes the intermediate product accumulation few, toxicity is low, good degrading effect.
(5) electrode activity height of the present invention, good stability.
Embodiment
Embodiment 1 preparation electrode
(1) batch mixing: the mixed that high purity graphite, 618 Resins, epoxy, 593 solidifying agent are pressed 100: 20: 5 (m/m/m).The actual employing of electrode preparation high purity graphite 20.00g, 618 Resins, epoxy 4.00g, 593 solidifying agent 1.00g in this experiment.Take by weighing high purity graphite powder 20.00g earlier, other takes by weighing 618 Resins, epoxy 4.00g, adds 593 solidifying agent 1.00g, adds acetone 10mL again, stirs to make Resins, epoxy fully dissolve mixing, is poured in the high purity graphite powder, fully stirs 10min, and it is mixed.
(2) compression moulding: the raw material that mixes is packed in the mould, and adopting internal diameter in this experiment is the mould of 1.7cm * 9.0cm, with 138.2N/cm
2Pressure compression moulding.
(3) solidify: the graphite rod after the compression moulding is sloughed mould, puts under the air at room temperature and places 12h, allows its spontaneous curing.
(4) baking: the graphite rod of moulding, curing back gained is put 150 ℃ of baking 2h down.
(5) activation: adopt electrochemical process that the graphite rod electrode of preparation is activated, make anode and negative electrode respectively with common graphite rod, be close to and it fastened on anode the graphite rod of preparation is parallel with anode with cotton thread, make positive terminal equal with graphite rod one end of preparation, the graphite rod of preparation place between the anode and cathode and with negative electrode at a distance of 0.5cm, to contain the acetone of 0.1M sodium acetate, anhydrous: water: the solution 250mL of Glacial acetic acid=50: 40: 10 (V/V/V) is an electrolytic solution, Glass Containers with the high 9.7cm of diameter 6.8cm is an electrolyzer, electrolysis voltage is 23.0V, and used for electrolyte heating in water bath constant temperature is at 25 ± 1 ℃.The electrolysis notch covers to prevent volatilization such as acetone with polyethylene film during electrolysis, only stays electrodes exposed outside, electrolysis treatment 10h.After electrolysis treatment finishes, graphite rod with 60mL acetone with the velocity axis of 0.6～0.8mL/min to drip washing.
(6) multiple baking: after drip washing finishes, graphite rod is placed 125 ℃ of baking 2h, so far, electrode preparation finishes.
Embodiment 2 preparation electrodes
(1) batch mixing: the mixed that high purity graphite, 616 Resins, epoxy, 701 solidifying agent are pressed 100: 30: 7.5 (m/m/m).The actual employing of electrode preparation high purity graphite 20.00g, 616 Resins, epoxy 6.00g, 701 solidifying agent 1.50g in this experiment.Take by weighing high purity graphite powder 20.00g earlier, other takes by weighing 616 Resins, epoxy 6.00g, adds 701 solidifying agent 1.50g, adds acetone 10mL again, stirs to make Resins, epoxy fully dissolve mixing, is poured in the high purity graphite powder, fully stirs 10min, and it is mixed.
(2) compression moulding: the raw material that mixes is packed in the mould, and adopting internal diameter in this experiment is the mould of 1.7cm * 9.0cm, with 138.2N/cm
2Pressure compression moulding.
(3) solidify: the graphite rod after the compression moulding is sloughed mould, puts under the air at room temperature and places 13h, allows its spontaneous curing.
(4) baking: the graphite rod of moulding, curing back gained is put 130 ℃ of baking 3h down.
(5) activation: adopt electrochemical process that the graphite rod electrode of preparation is activated, make anode and negative electrode respectively with common graphite rod, be close to and it fastened on anode the graphite rod of preparation is parallel with anode with cotton thread, make positive terminal equal with graphite rod one end of preparation, the graphite rod of preparation place between the anode and cathode and with negative electrode at a distance of 0.5cm, to contain the acetone of 0.1M sodium acetate, anhydrous: water: the solution 250mL of Glacial acetic acid=45: 45: 10 (V/V/V) is an electrolytic solution, Glass Containers with the high 9.7cm of diameter 6.8cm is an electrolyzer, electrolysis voltage is 23.0V, and used for electrolyte heating in water bath constant temperature is at 25 ± 1 ℃.The electrolysis notch covers to prevent volatilization such as acetone with polyethylene film during electrolysis, only stays electrodes exposed outside, electrolysis treatment 10h.After electrolysis treatment finishes, graphite rod with 60mL acetone with the velocity axis of 0.6～0.8mL/min to drip washing.
(6) multiple baking: after drip washing finishes, graphite rod is placed 115 ℃ of baking 3h, so far, electrode preparation finishes.
Be used from the electrolysis treatment of phenol-water solution with the Graphite Electrodes of the present invention preparation and common Graphite Electrodes one, relatively the performance of electrode and for the effect of phenol removal.Clearance, the variation of intermediate product, benzoquinones content with electrode pattern situation, phenol are standard.
Experiment is made anode with novel graphite resistor rod and the common graphite electrode of embodiment 1 respectively, and stainless steel 304 is made negative electrode, and the 200mg/L phenol 200mL that contains the 0.1M anhydrous sodium sulphate makes electrolytic solution, and current density is 18.9mA/cm
2, the electrolysis area is 20.65cm
2, cathode and anode spacing is 1.0cm, heating in water bath constant temperature stirs with magnetic force in the experimentation at 25 ± 1 ℃.
Test the removal effect of 1: two kind of electrolysis for phenol
Under above-mentioned electrolytic experiment condition, the common graphite electrode is 88.2% for the clearance of phenol, is higher than the novel graphite resistor rod 61.3% of preparation.
Test the variation of 2: two kinds of electrolysis phenol solution intermediate products
The middle aromatic product of phenol and degraded thereof, there is absorption in the district in UV-light (UV), studies the UV spectrum of degraded product, can understand the metamorphosis of phenol degrading product.Novel graphite resistor rod degraded product to common graphite electrode and preparation carries out UV scanning research.A little less than the oxidation susceptibility of common graphite electrode for phenol, it is undesirable to degrade, and a large amount of intermediate product accumulation is arranged and maintain higher concentration always; And the accumulation of novel graphite resistor rod intermediate product is few, good degrading effect.
Test the variation of 3: two kinds of electrolysis phenol solution benzoquinones
Benzoquinones is the intermediate product of phenol degrading, and has stronger toxicity and refractory organics than phenol.In the electrolytic process, the benzoquinones that the accumulation of common graphite electrode degrading is a large amount of, and be difficult to further degraded, its benzoquinones concentration is 43.8～31.2mg/L; And the benzoquinones concentration of novel graphite resistor rod when degraded accumulation is lower, and its concentration is 19.4～4.8mg/L.
Experiment 4: graphite is for the adsorption effect of phenol and benzoquinones
At 25 ℃, under the condition of neutral pH, graphite does not almost have adsorption for phenol, for the adsorption of para benzoquinone also extremely a little less than.This has just confirmed in the experiment of electrochemical degradation phenol, and the disappearance of phenol and intermediate product thereof is because the result of the electrochemical degradation effect of Graphite Electrodes, has also confirmed the electrochemical activity of novel graphite resistor rod and for the degradation capability of phenol.
The stability of testing 5: two kinds of electrodes compares
In the electrolytic process, loose coming off takes place in the common graphite electrode when electrolysis 1h, be easy to loss, and electrolysis finishes in the electrolytic solution of back a large amount of graphite granules is arranged, and the novel graphite resistor rod of preparation does not have loose obscission, and electrode is stablized no considerable change.Show that novel graphite resistor rod is stable, be more suitable for the electrochemical treatment of phenolic wastewater.
Claims (5)
1. Graphite Electrodes that is used for the phenolic wastewater electrochemical treatment, it is characterized in that this electrode is a main raw material with graphite, Resins, epoxy and solidifying agent, through mixing, moulding, curing, baking, activation with dry by the fire step preparation again and get, wherein said activation is an electrochemical activation;
When activating, make electrolytic solution, need be fixed on the anode by activated electrode, place and carry out electrolysis between anode and cathode, use acetone drip washing after the electrolysis with sodium acetate, anhydrous, acetone, water and Glacial acetic acid with the electrochemical process counter electrode; Described electrolytic solution is acetone, water and the acetum of 0.05～0.15mol/L sodium acetate, anhydrous, wherein the volume ratio of acetone, water and acetic acid is 55～45: 35～45: 10, electrochemical activation voltage is 22.0～24.0V, and electrode to be activated and cathode distance are 0.05～1.5cm;
Wherein the quality of Resins, epoxy is 10～30% of a graphite, and the quality of solidifying agent is 10～30% of a Resins, epoxy;
The solidified temperature is 15～35 ℃, and the time is 8～16h;
The temperature of baking is 130～170 ℃, and the time is 0.5～4h;
The temperature of multiple baking is 110～140 ℃, and the time is 0.5～4h.
2. Graphite Electrodes according to claim 1 is characterized in that described Resins, epoxy is 618 Resins, epoxy, 616 Resins, epoxy, 634 Resins, epoxy or 637 Resins, epoxy, and its quality is 10～30% of a graphite.
3. Graphite Electrodes according to claim 1 is characterized in that described solidifying agent is 593 solidifying agent, 590 solidifying agent, 701 solidifying agent, T-31 solidifying agent or T-33 solidifying agent.
4. Graphite Electrodes according to claim 1, the solvent when it is characterized in that mixing are acetone.
5. method for preparing the Graphite Electrodes that is used for the phenolic wastewater electrochemical treatment, it is characterized in that with graphite, Resins, epoxy and solidifying agent be main raw material, pass through mixing, moulding, curing, baking, activation and dry by the fire the step preparation again, wherein said activation is an electrochemical activation;
When activating, make electrolytic solution, need be fixed on the anode by activated electrode, place and carry out electrolysis between anode and cathode, use acetone drip washing after the electrolysis with sodium acetate, anhydrous, acetone, water and Glacial acetic acid with the electrochemical process counter electrode; Described electrolytic solution is acetone, water and the acetum of 0.05～0.15mol/L sodium acetate, anhydrous, wherein the volume ratio of acetone, water and acetic acid is 55～45: 35～45: 10, electrochemical activation voltage is 22.0～24.0V, and electrode to be activated and cathode distance are 0.05～1.5cm;
Wherein the quality of Resins, epoxy is 10～30% of a graphite, and the quality of solidifying agent is 10～30% of a Resins, epoxy;
The solidified temperature is 15～35 ℃, and the time is 8～16h;
The temperature of baking is 130～170 ℃, and the time is 0.5～4h;
The temperature of multiple baking is 110～140 ℃, and the time is 0.5～4h.
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| CN2008100187455A CN101302051B (en) | 2008-01-22 | 2008-01-22 | Graphite electrode for electrochemical treatment of phenolic waste water |
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| CN103073104B (en) * | 2013-01-30 | 2014-04-09 | 中国天辰工程有限公司 | Treatment method of caprolactam production waste water |
| WO2020205697A1 (en) * | 2019-03-29 | 2020-10-08 | Controlamatics Corporation | Process for producing highly activated electrode through electro-activation |
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| CN1927936A (en) * | 2005-09-08 | 2007-03-14 | 山东大学 | Modified phenolic resin/graphite based conducting composite material and preparation process thereof |
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