CN104803441A - Device and method of utilizing solar energy light-heat-electric coupling to treat acrylonitrile sewage - Google Patents
Device and method of utilizing solar energy light-heat-electric coupling to treat acrylonitrile sewage Download PDFInfo
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- CN104803441A CN104803441A CN201510221497.4A CN201510221497A CN104803441A CN 104803441 A CN104803441 A CN 104803441A CN 201510221497 A CN201510221497 A CN 201510221497A CN 104803441 A CN104803441 A CN 104803441A
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- vinyl cyanide
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- 238000000034 method Methods 0.000 title claims abstract description 54
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000010168 coupling process Methods 0.000 title abstract description 11
- 230000008878 coupling Effects 0.000 title abstract description 10
- 238000005859 coupling reaction Methods 0.000 title abstract description 10
- 239000010865 sewage Substances 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 22
- 230000015556 catabolic process Effects 0.000 claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 claims abstract description 15
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 3
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 229920002401 polyacrylamide Polymers 0.000 abstract 2
- 239000007832 Na2SO4 Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 39
- -1 acrylic nitrile Chemical class 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000011282 treatment Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000006056 electrooxidation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000010815 organic waste Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000003851 biochemical process Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009284 supercritical water oxidation Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920013649 Paracril Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AIDQCFHFXWPAFG-UHFFFAOYSA-N n-formylformamide Chemical compound O=CNC=O AIDQCFHFXWPAFG-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 231100000289 photo-effect Toxicity 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a device and method of utilizing solar energy light-heat-electric coupling to treat acrylonitrile sewage. The device comprises a solar energy light-heat-electricity conversion system, wherein the solar energy light-heat-electricity conversion system comprises a photo-thermal unit, a photoelectric unit and an electrochemical unit; the photo-thermal unit comprises a focusing lens for adjusting the temperature of the electrochemical unit; the photoelectric unit adopts a photocell; the electrochemical unit adopts an electrolytic tank. The method comprises the following steps: 1) constructing the device for degrading polyacrylamide; 2) adjusting the photo-thermal unit and the photoelectric unit; 3) performing the electrolytic process in a diaphragm-free electrolytic cell, wherein the electrolytic process is completed according to the constant voltage of 3-10 V, the electrolyte of the electrolytic solution is 5-20 g/L of Na2SO4, the pH value of the electrolytic solution is 4-12, the temperature is 20 DEG C above, the polyacrylamide solution is gradually added into the electrolyte. The device and method disclosed by the invention are simple and practical, high in degradation rate, energy-saving and environmentally friendly.
Description
Technical field
The present invention relates to during exploitation of oil-gas field and Chemicals manufacture the technical field of sewage produced, particularly a kind of device and method utilizing solar energy-Re-electric coupling oxide treatment vinyl cyanide trade effluent.
Background technology
Vinyl cyanide (acrylonitrile, AN) productions such as acrylic fibers, paracril, adiponitrile, acrylamide, ABS resin are mainly used in, the basic raw material of three large synthetic materialss (synthon, plastics, synthetic rubber), extensive in organic synthesis industrial use.In recent years, along with downstream synthetic materials demand constantly increases, China's vinyl cyanide production capacity and output obtained fast lifting.In the production process of vinyl cyanide, there is a large amount of trade effluent containing toxic substances such as vinyl cyanide, prussic acid, acetonitriles to produce, as not treated direct discharge, comparatively major injury can be caused to human body and animals and plants.Due to high hazardness and the refractory organics of acrylic nitrile waste water, seeking suitable treatment process becomes one of difficult problem that Now Domestic generally acknowledges outward.
For vinyl cyanide Industrial Waste Water Treatments, current industrial applications is burning method, pressurized hydrolysis and Wet Catalytic Oxidation Method etc. the most widely.There is the problem consuming a large amount of auxiliary fuel oil and secondary pollution in burning method; The domestic employing of pressurizing hydrolysis is more, but pollutes and ammonia nitrogen problem because its polymkeric substance removal efficiency is low, there is soda acid, is substantially eliminated abroad; Wet Catalytic Oxidation Method uses because the price of expensive catalyst also limit it, and its reaction conditions requires higher to equipment material, and investment is large, causes the effect of commercial introduction also not satisfactory.In addition also have biochemical process and active carbon adsorption, biochemical process is only suitable for the acrylic nitrile waste water processing lower concentration, generally need carry out pre-treatment to improve the biodegradable of waste water, have larger complicacy and limitation compared with burning method; Active carbon adsorption need with additive method conbined usage, and the regeneration of gac adds the complicacy of operation.
In view of the ubiquitous shortcomings and limitations of aforesaid method, some emerging treatment processs are arisen at the historic moment, as supercritical water oxidation method, electrochemical oxidation process, membrane separation process etc.Supercritical water oxidation method requires the reaction conditions of High Temperature High Pressure, requires strict to equipment material, and general investment is larger.Electrochemical oxidation all has good treatment effect to useless Organic substance in water, ammonia nitrogen and colourity, both can be used as the method for advanced treatment, also can be used as a kind of pretreatment process, but higher energy consumption limits the widespread use of this method in engineering.For membrane separation process, the film preparation that cheap, performance is complete and the stained problems affect of film the widespread use of this method, and, separate from waste water, and unrealized it thoroughly to be degraded, still need subsequent disposal to make it reach real innoxious.
Such as, publication number is the Chinese patent application of CN103663875A, it discloses a kind of method improving denitrification rate of acrylonitrile waste water, mainly processes acrylic nitrile waste water in solution prior art and there is the problem that removal efficiency is lower, water outlet COD or TN is not up to standard.This invention is by adopting a kind of method improving denitrification rate of acrylonitrile waste water, and first (1) acrylic nitrile waste water enters short-cut nitrification and denitrification pond; (2) effluent in described short-cut nitrification and denitrification pond enters anoxic pond; (3) effluent of described anoxic pond enters first stage precipitation tank, and top effluent enters Aerobic Pond, and base sludge is at least partially as mud discharging; (3) effluent of described Aerobic Pond enters second-level settling pond, and supernatant liquor enters advanced oxidation pond, and base sludge discharges; (4) effluent in described advanced oxidation pond enters BAF, and the standard water discharge discharge of (5) described BAF, the technical scheme of the mud discharging of generation can be used in the industrial treatment of acrylic nitrile waste water.
Publication number is the Chinese patent application of CN103159374A, and it discloses a kind for the treatment of process to the organic waste water containing vinyl cyanide material, it comprises the following step: (1) materializing strategy; (2) anoxic/aerobic (A/O) biochemical treatment; (3) deep oxidation process, obtains process water outlet.This treatment process can effectively process produce in polyacrylonitrile production process containing the high density of vinyl cyanide material, the organic waste water of difficult degradation, process water outlet can qualified discharge or direct reuse in production process.
Publication number is the Chinese patent application of CN102531132A, it discloses a kind of COD degradation agent preparation and application thereof of removing vinyl cyanide in waste water, the preparation method of degradation agents is: (1) mixes a certain amount of nickel oxide in 120 ~ 200 order volcanic ash pulverized, and adds suitable quantity of water and be adjusted to pasty state after mixing; (2) add a certain proportion of polycyclic oxygen amber glass acid sodium and azo isopropyl acid diformamide again, under 300 DEG C ~ 400 DEG C high temperature, calcine 120 ~ 300 minutes, obtain porous honeycomb solid; (3) above-mentioned cellular solids material is soaked 5 ~ 10 hours in the fumaric acid of 50 ~ 100mg/L, then oven dry under the protection of nitrogen, pulverizing can obtain required COD degradation agent.During use, degradation agents of the present invention with seamless spin cloth parcel after, be placed in open column shape container, regulate acrylic nitrile waste water pH to be 4.0 ~ 6.0, make waste water from bottom to top by this container, and with ultrasonic oscillation.Degradation agents of the present invention has the vinyl cyanide in highly selective removal waste water, and treatment effect is not by other Pollutant effects in water.After empirical tests adopts degradation agents process waste water of the present invention, the vinyl cyanide in waste water can be stablized and reaches wastewater discharge standard.
In sum, although the method that acrylic nitrile waste water is administered is of a great variety, most methods is all difficult to show consideration for environmental effect and economic benefit, or exist like this, such shortcoming and difficult in industrialization promotion.
Solar energy-Re-electrochemical couple method (solar thermal electrochemical production, be called for short STEP) be take all sun power as the energy, utilize light-electricity-heating integrated coupling by vinyl cyanide organic waste water oxidative degradation process simultaneously.And sun power is a kind of free of contamination green energy resource of optimal new millennium, be the cleanest and inexhaustible natural energy resources, there is clean, safe and continuable feature.Therefore, the proposition tool of this efficient, green, economic acrylic nitrile waste water administering method is of great significance.
Summary of the invention
The invention provides a kind of vinyl cyanide sewage disposal technology, this technology has green, environmental protection, energy-conservation feature.STEP technology take all sun power as the energy, utilizes light-electricity-heating integrated coupling by vinyl cyanide organic waste water oxidative degradation process simultaneously.And sun power is a kind of free of contamination green energy resource of optimal new millennium, be the cleanest and inexhaustible natural energy resources, there is clean, safe and continuable feature.Solve catalytic oxidation operational path complicated, consume energy large shortcoming.
The structure of STEP system is one of content of invention.STEP system is divided into three unit, is light-hot cell, light-electric unit, electrochemical cell respectively.
Light-hot cell is exactly Solar Energy Heat Utilization System, when this laboratory study, adopts solar energy stove (as 5 in Fig. 3) to carry out adjustment System reaction temperature required.
Light-electric unit selects multistage silica-based solar cell, the single basic silicon based opto-electronics pool unit of this experiment employing realizes the conversion between sun power and electric energy, the electric energy be converted to is made to reach electroaffinity necessary requirement, regulate focusing system (as 6 in Fig. 3), the coupling of adjustment between energy level/energy, spectrum, electromotive force and efficiency simultaneously.
In electrochemical cell, energy derive is not only photocell and is make use of visible and ultraviolet region with photovoltaic effect, also utilizes infrared and far infrared region with photo-thermal effect, greatly improves Solar use efficiency.By solar panel as system direct supply, solar energy condensation board provides hot environment for system, ensures homo(io)thermism by adjustment focal point position.Voltage usable direct current transformer from solar panel is finely tuned, and controls and detects simultaneously with reometer and voltmeter.In this unit, vinyl cyanide organic sewage is degraded.
These three unit are coupled by STEP technology exactly, take sun power as the energy, utilize light-Re, light-electricity and self photoeffect and corresponding three grades of effects thereof realize the coupling matching (see Fig. 2) of vertical and horizontal, utilize its collaborative coupling each other (as controlled temperature of reaction by light-hot cell, temperature of reaction adjustment electrochemical oxidation current potential, electrochemical oxidation current potential feedback adjustment light-electric unit electromotive force, light-electric unit and light-hot cell are optimized and revised mutually, reach maximum Solar use efficiency and electrolytic efficiency), importantly photo-thermal effect can make electrochemical oxidation reactions carry out at relatively high temperatures, and the redox-potential of anode also variation with temperature and changing, therefore light-hot cell can be utilized to regulate temperature, thus the voltage of adjustment electrochemical cell, make it mate with the current potential of light-electric unit to circulate, thus efficient degradation treatment is carried out to vinyl cyanide.
The selection of anode material, this invention is by contrast Ti/ (IrO
2aMP.AMp.Amp Ta
2o
5) electrode, Ti/ (RuO
2aMP.AMp.Amp IrO
2) electrode, Ti/ (SnO
2aMP.AMp.Amp Sb
2o
3) the electrode anode material different with Graphite Electrodes these four on the impact of vinyl cyanide degradation effect, therefrom have selected the anode electrode of the most applicable vinyl cyanide organic sewage process, i.e. Ti/ (IrO
2aMP.AMp.Amp Ta
2o
5) electrode.
Based on the high-temperature electrolysis method of above-mentioned solar energy-Re-electric coupling oxide treatment vinyl cyanide system, it is characterized in that: the method comprises the steps:
(1) electrochemical cell of negative electrode, anode, electrolyzer and ionogen composition is built;
(2) provide electric energy by light-electric unit, light-hot cell provides hot environment for reacting;
(3) electrolyzer homo(io)thermism is controlled at about 90 DEG C;
(4) control direct supply current constant at 50mA, reaction 1h-2h, main reaction is that vinyl cyanide complete oxidation is produced CO
2, main reaction is: C
3h
3n (l)+9H
2o (l) → 3CO
2(g)+HNO
3+ 20H
2g (), also comprises the competing reaction of water in electrolytic process, react to be: H
2o (l) → 1/2O
2(g)+H
2(g).
The mechanism of main reaction is:
Anodic reaction: C
3h
3n (l)+9H
2o (l) → 3CO
2(g)+NO
3 -+ 21H
+(l)+20e
-
Cathodic reaction: 20H
+(l)+20e
-→ 10H
2(g)
Completed cell is reacted: C
3h
3n (l)+9H
2o (l) → 3CO
2(g)+HNO
3+ 10H
2(g)
Particularly, the invention provides a kind of device for vinyl cyanide degraded, comprise solar energy-Re-power conversion system, described solar energy-Re-point converting system comprises light-hot cell, light-electric unit and electrochemical cell, described photo-thermal unit comprises the solar energy stove for regulating electrochemical cell temperature, photovoltaic element is photocell, and electrochemical cell is electrolyzer.
Further, described photocell is multistage silica-based solar cell.
Further, the anode in described electrochemical cell adopts Ti/ (IrO
2aMP.AMp.Amp Ta
2o
5) electrode, negative electrode adopts platinum electrode.
Present invention also offers a kind of method of vinyl cyanide of degrading, it is characterized in that, comprise the following steps:
1) device reduced for vinyl cyanide as described in any one of claim 1-3 is built;
2) regulate light-hot cell, light-electric unit, provide electric energy by light-electric unit, light-hot cell provides hot environment for reacting;
3) in undivided cell, carry out electrolytic process, control direct supply current constant at 50mA, 0.5h-2h is to complete electrolysis in reaction, the ionogen Na of electrolytic solution
2sO
4, pH=4 ~ 12, temperature is more than 50 DEG C.
Further, the Na of the ionogen of described electrolytic solution to be concentration be 3-10g/L
2sO
4, preferred concentration is the Na of 5g/L
2sO
4.
Further, the pH of described electrolytic solution is 3-7, and preferred pH is 3,4,5,6,7 or its middle arbitrary value.
Further, the temperature of described electrolytic solution be 50 DEG C and more than, or 55 DEG C and more than, or 65 DEG C and more than, or 70 DEG C and more than, or 75 DEG C and more than, or 80 DEG C and more than, or 85 DEG C and more than, or 90 DEG C and more than, be preferably 50-100 DEG C, be more preferably 85-95 DEG C, most preferably be 90 DEG C.
Further, the time of electrolysis is 1-2h.
Present invention also offers a kind of testing apparatus for detecting organic matter degradation, it is characterized in that, comprise solar energy-Re-power conversion system, described solar energy-Re-point converting system comprises photo-thermal unit, photovoltaic element and electrochemical cell, the light source of simulated solar, and analytical instrument, described photo-thermal unit comprises the condenser lens for regulating electrochemical cell temperature, photovoltaic element is photocell, and electrochemical cell is electrolyzer.
Further, described organism is vinyl cyanide.
Accompanying drawing explanation
The electrochemical experimental device figure of Fig. 1 shop experiment
In figure: 1-magnetic rotor; 2-digital display heat-collecting magnetic stirring device; 3-negative electrode; 4-anode; 5-electrochemical workstation
The coupled mode figure of Fig. 2 Solar use
In figure: 1-sun power; 2-light (one-level); 3-heat (secondary); 4-electricity (secondary); 5-heat; 6-pyrolysis; 7-photodissociation; 8-photosensitization; 9-photochemical catalysis; 10-electric field; 11-electrochemistry; 12-pollutent water-in; 13-water water outlet up to standard; 14-Longitudinal data; 15-lateral
The circuit connection diagram of the outdoor experimental installation of Fig. 3
In figure: 1-sun power; 2-water outlet; 3-water-in; 4-reactor; 5-condensor; 6-photovoltaic module
After the degraded of Fig. 4 Different electrodes, acrylonitrile concentration is with the change in reaction times
Embodiment
The preparation of vinyl cyanide simulated sewage:
(1) measure appropriate vinyl cyanide, be mixed with the storing solution of 1000mg/L by water dissolution, under being kept at 4 DEG C of conditions, during use, be diluted to desired concn.
(2) take appropriate sodium sulfate, become the ionogen storing solution of 50g/L by water dissolution, during use, be diluted to desired concn.The sodium sulfate concentration wherein adopted in example is 5g/L.
001 shop experiment research:
As shown in Figure 1, in employing Fig. 1,2 provide the temperature needed for electrolysis and continue to stir the indoor electrolyzer of this experiment, use the acrylonitrile electrolysis liquid that homemade Glass Containers mixes as electrolyzer splendid attire simultaneously.Experiment adopts two electrodes system, and negative electrode (as 3 in Fig. 1) adopts pure platinum electrode, and anode (as 4 in Fig. 1) adopts Ti/ (IrO
2aMP.AMp.Amp Ta
2o
5) electrode.Explore the impact of each factor on vinyl cyanide sun power STEP degradation effect, main thought is exactly adopt the method controlling unitary variant to explore the impact of each influence factor on vinyl cyanide degradation effect.Obtain the processing condition of sun power STEP process oxidative degradation vinyl cyanide the best thus.
Example 1: anode adopts Ti/ (IrO
2aMP.AMp.Amp Ta
2o
5) electrode, negative electrode adopts platinum electrode, with 6mA/cm
2current density, the reaction times is 40min, pH=3, and temperature of reaction is 50 DEG C, degrades to the acrylic nitrile waste water of concentration 200mg/L, acrylic nitrile waste water degraded after COD clearance be 48%.
Example 2: anode adopts Ti/ (IrO
2aMP.AMp.Amp Ta
2o
5) electrode, negative electrode adopts platinum electrode, with 6mA/cm
2current density, the reaction times is 1h, pH=7, and temperature of reaction is 50 DEG C, degrades to the acrylic nitrile waste water of concentration 200mg/L, acrylic nitrile waste water degraded after COD clearance be 47.1%.
Example 3: anode adopts Ti/ (IrO
2aMP.AMp.Amp Ta
2o
5) electrode, negative electrode adopts platinum electrode, with 6mA/cm
2current density, the reaction times is 1h, pH=7, and temperature of reaction is 70 DEG C, degrades to the acrylic nitrile waste water of concentration 200mg/L, acrylic nitrile waste water degraded after COD clearance be 54.4%.
Example 4: anode adopts Ti/ (IrO
2aMP.AMp.Amp Ta
2o
5) electrode, negative electrode adopts platinum electrode, with 6mA/cm
2current density, the reaction times is respectively 2h, pH=7, and temperature of reaction is 50 DEG C, degrades to the acrylic nitrile waste water of concentration 200mg/L, acrylic nitrile waste water degraded after COD clearance be 57.6%.
Example 5: anode adopts Ti/ (IrO
2aMP.AMp.Amp Ta
2o
5) electrode, negative electrode adopts platinum electrode, with 6mA/cm
2current density, the reaction times is 1h, pH=7, and temperature of reaction is 90 DEG C, degrades to the acrylic nitrile waste water of concentration 200mg/L, acrylic nitrile waste water degraded after COD clearance be 67%.
Example 6: anode adopts Graphite Electrodes, negative electrode adopts platinum electrode, with 6mA/cm
2current density, the reaction times is respectively 2h, pH=7, and temperature of reaction is 50 DEG C, degrades to the acrylic nitrile waste water of concentration 100mg/L, acrylic nitrile waste water degraded after vinyl cyanide clearance be 60.9%.
Example 7: anode adopts Ti/IrO
2aMP.AMp.Amp Ta
2o
5electrode, negative electrode adopts platinum electrode, with 6mA/cm
2current density, the reaction times is respectively 2h, pH=7, and temperature of reaction is 50 DEG C, degrades to the acrylic nitrile waste water of concentration 100mg/L, acrylic nitrile waste water degraded after vinyl cyanide clearance be 67.5%.
Example 8: anode adopts Ti/RuO
2aMP.AMp.Amp IrO
2electrode, negative electrode adopts platinum electrode, with 6mA/cm
2current density, the reaction times is respectively 2h, pH=7, and temperature of reaction is 50 DEG C, degrades to the acrylic nitrile waste water of concentration 100mg/L, acrylic nitrile waste water degraded after vinyl cyanide clearance be 62.9%.
Experiment 9: anode adopts Ti/SnO
2aMP.AMp.Amp Sb
2o
3electrode, negative electrode adopts platinum electrode, with 6mA/cm
2current density, the reaction times is respectively 2h, pH=7, and temperature of reaction is 50 DEG C, degrades to the acrylic nitrile waste water of concentration 100mg/L, acrylic nitrile waste water degraded after vinyl cyanide clearance be 58.6%.
002 outdoor test research:
Adopt the outdoor location of STEP technology oxide treatment acrylic nitrile waste water as shown in Figure 3.In light-hot cell, solar energy stove (as 5 in Fig. 3) is adopted to carry out adjustment System reaction temperature required.Single basic silicon based opto-electronics pool unit is adopted in light-electric unit, realize the conversion between sun power and electric energy, the electric energy be converted to is made to reach electroaffinity necessary requirement, regulate focusing system (as 6 in Fig. 3), the coupling of adjustment between energy level/energy, spectrum, electromotive force and efficiency simultaneously.
Example 10: with Ti/ (IrO
2aMP.AMp.Amp Ta
2o
5) electrode is anode, pure platinum electrode is negative electrode, and effective surface electrode is long-pending is 8cm
2, pH=3, Na
2sO
4electrolyte concentration is 5g/L, is to process the acrylic nitrile waste water that concentration is 100mg/L under the condition of 90 DEG C in temperature of reaction, and the reaction times is 30min, and after acrylic nitrile waste water degraded, COD clearance is 49.8%.
Claims (10)
1. the device for vinyl cyanide degraded, it is characterized in that, comprise solar energy-Re-power conversion system, described solar energy-Re-point converting system comprises light-hot cell, light-electric unit and electrochemical cell, described photo-thermal unit comprises the solar energy stove for regulating electrochemical cell temperature, photovoltaic element is photocell, and electrochemical cell is electrolyzer.
2. the device for vinyl cyanide degraded according to claim 1, it is characterized in that, described photocell is multistage silica-based solar cell.
3. the device for vinyl cyanide degraded according to any one of claim 1-2, is characterized in that, the anode in described electrochemical cell adopts Ti/ (IrO
2aMP.AMp.Amp Ta
2o
5) electrode, negative electrode adopts platinum electrode.
4. to degrade the method for vinyl cyanide, it is characterized in that, comprise the following steps:
1) device reduced for vinyl cyanide as described in any one of claim 1-3 is built;
2) regulate light-hot cell, light-electric unit, provide electric energy by light-electric unit, light-hot cell provides hot environment for reacting;
3) in undivided cell, carry out electrolytic process, control direct supply current constant at 50mA, 0.5h-2h is to complete electrolysis in reaction, the ionogen Na of electrolytic solution
2sO
4, pH=4 ~ 12, temperature is more than 50 DEG C.
5. the method for degraded vinyl cyanide according to claim 4, the Na of the ionogen of described electrolytic solution to be concentration be 3-10g/L
2sO
4, preferred concentration is the Na of 5g/L
2sO
4.
6. the method for the degraded vinyl cyanide according to any one of claim 4-5, the pH of described electrolytic solution is 3-7, and preferred pH is 3,4,5,6,7 or its middle arbitrary value.
7. the method for the degraded vinyl cyanide according to any one of claim 4-6, the temperature of described electrolytic solution be 50 DEG C and more than, or 55 DEG C and more than, or 65 DEG C and more than, or 70 DEG C and more than, or 75 DEG C and more than, or 80 DEG C and more than, or 85 DEG C and more than, or 90 DEG C and more than, be preferably 50-100 DEG C, be more preferably 85-95 DEG C, most preferably be 90 DEG C.
8. the method for the degraded vinyl cyanide according to any one of claim 4-6, the time of electrolysis is 1-2h.
9. one kind for detecting the testing apparatus of organic matter degradation, it is characterized in that, comprise solar energy-Re-power conversion system, described solar energy-Re-power conversion system comprises photo-thermal unit, photovoltaic element and electrochemical cell, the light source of simulated solar, and analytical instrument, described photo-thermal unit comprises the condenser lens for regulating electrochemical cell temperature, photovoltaic element is photocell, and electrochemical cell is electrolyzer.
10. as claimed in claim 9 for detecting the testing apparatus of organic matter degradation, it is characterized in that, described organism is vinyl cyanide.
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