CN104803441B - A kind of method of solar energy coupled thermomechanics processing acrylonitrile sewage - Google Patents
A kind of method of solar energy coupled thermomechanics processing acrylonitrile sewage Download PDFInfo
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- CN104803441B CN104803441B CN201510221497.4A CN201510221497A CN104803441B CN 104803441 B CN104803441 B CN 104803441B CN 201510221497 A CN201510221497 A CN 201510221497A CN 104803441 B CN104803441 B CN 104803441B
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- acrylonitrile
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000012545 processing Methods 0.000 title description 8
- 239000010865 sewage Substances 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 26
- 230000003287 optical effect Effects 0.000 claims description 18
- 230000005693 optoelectronics Effects 0.000 claims description 16
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 20
- 238000006731 degradation reaction Methods 0.000 abstract description 20
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 4
- 239000007832 Na2SO4 Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 description 37
- -1 alkene nitrile Chemical class 0.000 description 23
- 210000004027 cell Anatomy 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 230000000694 effects Effects 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 230000008878 coupling Effects 0.000 description 8
- 238000010168 coupling process Methods 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006056 electrooxidation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000003851 biochemical process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 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
- 238000009533 lab test Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GUYXXEXGKVKXAW-UHFFFAOYSA-N prop-2-enenitrile Chemical compound C=CC#N.C=CC#N GUYXXEXGKVKXAW-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 235000011152 sodium sulphate Nutrition 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
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method 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
- LYZABRCOWKBYEI-UHFFFAOYSA-N C(=O)N.C(=O)N.C(CC)(=O)O Chemical compound C(=O)N.C(=O)N.C(CC)(=O)O LYZABRCOWKBYEI-UHFFFAOYSA-N 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
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [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
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000012412 chemical coupling Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 230000006872 improvement Effects 0.000 description 1
- 208000014674 injury Diseases 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
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 210000004508 polar body Anatomy 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- 241000894007 species Species 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009284 supercritical water oxidation 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
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 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 present invention relates to a kind of method of solar energy optical-thermal electrochemical degradation acrylonitrile, the step of methods described is 1) to build the device for acrylonitrile degraded, device for acrylonitrile degraded includes solar energy thermoelectric conversion system, the solar energy thermoelectric conversion system includes photo-thermal unit, photovoltaic element and electrochemical cell, the photo-thermal unit includes being used for the condenser lens for adjusting electrochemical cell temperature, photovoltaic element is photocell, and electrochemical cell is electrolytic cell；2) photo-thermal unit, photovoltaic element are adjusted；3) electrolytic process is carried out in undivided cell, 3~10V constant voltage electrolysis completion, the electrolyte of electrolytic solution is 5 20g/L Na2SO4, pH=4~12, temperature be more than 20 DEG C, be gradually added acrylonitrile solution in the electrolyte.The method simple practical of the present invention, degradation rate is high, energy-conserving and environment-protective.
Description
Technical field
Caused technical field of sewage in being manufactured the present invention relates to exploitation of oil-gas field and chemical products, more particularly to
A kind of method that oxidation processes acrylonitrile industrial wastewater is coupled using solar energy-thermo-electrically.
Background technology
Acrylonitrile (acrylonitrile, AN) is mainly used in acrylic fibers, nitrile rubber, adiponitrile, acrylamide, ABS resin
Deng production, be three big synthetic materials (synthetic fibers, plastics, synthetic rubber) base stock, it is wide in organic synthesis industrial use
It is general.In recent years, as downstream synthetic material demand constantly increases, China's acrylonitrile production capacity and yield obtain fast lifting.Third
In the production process of alkene nitrile, there is largely that industrial wastewater containing noxious materials such as acrylonitrile, hydrogen cyanide, acetonitriles produces, such as without
Processing is directly discharged, and human body and animals and plants can be caused compared with major injury.Due to the high harmfulness and refractory organicses of acrylic nitrile waste water,
Seek suitable processing method as one of problem generally acknowledged outside Now Domestic.
For acrylonitrile Industrial Waste Water Treatments, industrial applications are most widely burning method, pressurized hydrolysis and wet type at present
Catalytic oxidation etc..The problem of consuming a large amount of auxiliary fuel oil and secondary pollution be present in burning method；Pressurizing hydrolysis are domestic to be used
It is more, but because of its, polymer removal efficiency is low, soda acid pollution and ammonia nitrogen be present, is eliminated substantially abroad；Wet type is urged
Change oxidizing process because the price of expensive catalyst also limit its use, and its reaction condition requires higher to equipment material, throws
Money is big, causes the effect of commercial introduction also not satisfactory.In addition with biochemical process and active carbon adsorption, biochemical process is only suitable for
The acrylic nitrile waste water of low concentration is handled, need to typically be pre-processed to improve the biodegradable of waste water, had more compared with burning method
Big complexity and limitation；Active carbon adsorption need to be used in combination with other method, and the regeneration of activated carbon adds process
Complexity.
In view of the shortcomings that above method generally existing and limitation, some emerging processing methods are arisen at the historic moment, such as super to face
Boundary's water oxidation, electrochemical oxidation process, membrane separation process etc..Supercritical water oxidation method requires the reaction condition of HTHP, pair sets
Standby material requirement is strict, typically invests larger.Electrochemical oxidation has good processing to useless Organic substance in water, ammonia nitrogen and colourity
Effect, the method that can not only be used for advanced treating, a kind of preprocess method is can act also as, but higher energy consumption limits the method in work
Extensive use in journey.For membrane separation process, the film preparation cheap, performance is complete and film are stained problem and affect the method
Extensive use, moreover, being separated from waste water, and it is not implemented to its thorough degraded, still needs to subsequent treatment and reach really
It is innoxious.
For example, Publication No. CN103663875A Chinese patent application, improves acrylic nitrile waste water it discloses one kind and takes off
The method of nitrogen rate, mainly solve to handle acrylic nitrile waste water in the prior art and have that removal efficiency is relatively low, water outlet COD or TN be not up to standard
The problem of.The invention initially enters short distance by using a kind of method for improving denitrification rate of acrylonitrile waste water, (1) acrylic nitrile waste water
Nitration denitrification pond；(2) effluent in the short-cut nitrification and denitrification pond enters anoxic pond；(3) effluent of the anoxic pond
Into first stage precipitation tank, top effluent enters Aerobic Pond, and base sludge at least a portion is used as mud discharging；(3) it is described good
The effluent in oxygen pond enters second-level settling pond, and supernatant enters advanced oxidation pond, base sludge discharge；(4) advanced oxidation
The effluent in pond enters BAF, and the standard water discharge of (5) described BAF is discharged, caused mud discharging
Technical scheme can be used in the industrial treatment of acrylic nitrile waste water.
Publication No. CN103159374A Chinese patent application, it discloses a kind of to the organic of the material containing vinyl cyanide
The handling process of waste water, it is comprised the steps of：(1) materializing strategy；(2) anoxic/aerobic (A/O) biochemical treatment；(3) depth oxygen
Change is handled, and produces processing water outlet.The handling process can effectively handle caused thing containing vinyl cyanide in polyacrylonitrile production process
The high concentration of matter, the organic wastewater of difficult degradation, processing water outlet can qualified discharge or direct reuse in production process.
Publication No. CN102531132A Chinese patent application, it discloses a kind of COD for removing acrylonitrile in waste water
Prepared by degradation agent and its application, the preparation method of degradation agent are：(1) mixed into 120~200 mesh volcanic ash of crushing a certain amount of
Nickel oxide, after mixing add suitable quantity of water be adjusted to pasty state；(2) it is different that a certain proportion of polycyclic oxygen amber glass acid sodium and azo are added
Propionic acid diformamide, under 300 DEG C~400 DEG C high temperature, calcine 120~300 minutes, obtain porous honeycomb solid；(3) upper
State cellular solids material to soak 5~10 hours in 50~100mg/L fumaric acid, then dried under the protection of nitrogen
Dry, crushing can obtain required COD degradation agent.In use, degradation agent of the present invention is placed in hollow with after seamless spinning cloth parcel
In column shape container, regulation acrylic nitrile waste water pH is 4.0~6.0, makes waste water from bottom to top by the container, and is shaken with ultrasonic wave
Swing.Degradation agent of the present invention has the acrylonitrile removed with high selectivity in waste water, treatment effect not other pollutants in by water
Influence.After empirical tests are using the degradation agent processing waste water of the present invention, the acrylonitrile in waste water can stably reach wastewater discharge standard.
In summary, although the method species of acrylic nitrile waste water improvement is various, most methods are all difficult to show consideration for environment
Effect and economic benefit, or exist so, it is such the shortcomings that and it is difficult in industrialization promotion.
Solar energy-thermo-electrically chemical Coupling method (solar thermal electrochemical production, letter
STEP) be referred to as all the energy using solar energy, while using optical-electronic-heating integrated coupling by acrylonitrile organic waste water oxygen
Change degradation treatment.It is most clean and inexhaustible and solar energy is a kind of free of contamination green energy resource of optimal new century
Natural energy resources, have cleaning, safe and sustainable feature.Therefore, this acrylic nitrile waste water efficiently, green, economic is controlled
The it is proposed tool of reason method is of great significance.
The content of the invention
The invention provides a kind of acrylonitrile sewage disposal technology, the technology has the characteristics of green, environmental protection, energy-conservation.
STEP technologies are all using solar energy as the energy, while using optical-electronic-heating integrated coupling by acrylonitrile organic waste water oxygen
Change degradation treatment.It is most clean and inexhaustible and solar energy is a kind of free of contamination green energy resource of optimal new century
Natural energy resources, have cleaning, safe and sustainable feature.Solve electrocatalytic oxidation process route complexity, consume energy big
Shortcoming.
The structure of STEP systems is one of content of invention.STEP systems are divided into three units, be respectively optical and thermal unit,
Opto-electronic element, electrochemical cell.
Optical and thermal unit is exactly Solar Energy Heat Utilization System, in this laboratory research, using solar energy stove (in Fig. 3
5) temperature needed for system response is adjusted.
Opto-electronic element selects multistage silica-based solar cell, and this experiment is realized using single basic silicon based opto-electronicses pool unit
Conversion between solar energy and electric energy, the electric energy for making to be converted to reaches electroaffinity necessary requirement, while adjusts focusing system
(6 in such as Fig. 3), the matching between adjustment energy level/energy, spectrum, potential and efficiency.
In electrochemical cell, energy source is not only photocell and make use of visible and ultra-violet (UV) band with photoelectric effect, also with
Photo-thermal effect utilizes infrared and far-infrared band, greatly improves Solar use efficiency.By solar panel as system direct current
Power supply, solar energy condensation board provide hot environment for system, ensure that temperature is constant by adjusting focal point position.From solar energy
The voltage of cell panel can be finely tuned with commutator transformer, while controlled and detected with ammeter and voltmeter.In this unit
Middle acrylonitrile organic sewage is degraded.
STEP technologies are exactly coupled these three units, using solar energy as the energy, using optical and thermal, optical-electronic and itself
Luminous effect and its effect of corresponding three-level realize the coupling matchings (see Fig. 2) of vertical and horizontal, utilize its mutual association
Same coupling (such as passes through optical and thermal unit controlling reaction temperature, reaction temperature adjustment electrochemical oxidation current potential, electrochemical oxidation
Current potential feedback adjustment opto-electronic element potential, opto-electronic element are mutually optimized and revised with optical and thermal unit, reach maximum solar energy profit
With efficiency and electrolytic efficiency), it is important that photo-thermal effect can be such that electrochemical oxidation reactions carry out at relatively high temperatures, and anode
Redox potential also variation with temperature and change, therefore using optical and thermal unit adjust temperature, so as to adjust electrochemistry
The voltage of unit, it is set to match circulation with the current potential of opto-electronic element, so as to carry out efficient degradation treatment to acrylonitrile.
The selection of anode material, this invention is by contrasting Ti/ (IrO2&Ta2O5) electrode, Ti/ (RuO2&IrO2) electrode,
Ti/(SnO2&Sb2O3) electrode and graphite electrode this influence of four different anode materials to acrylonitrile degradation effect, Cong Zhongxuan
The anode electrode of most suitable acrylonitrile organic sewage processing, i.e. Ti/ (IrO are gone out2&Ta2O5) electrode.
Based on the high-temperature electrolysis method of above-mentioned solar energy-thermo-electrically coupling oxidation processes acrylonitrile system, its feature exists
In：This method comprises the following steps：
(1) electrochemical cell of negative electrode, anode, electrolytic cell and electrolyte composition is built；
(2) electric energy is provided by opto-electronic element, optical and thermal unit provides hot environment for reaction；
(3) control electrolytic cell temperature constant at 90 DEG C or so；
(4) control dc source electric current constant in 50mA, react 1h-2h, main reaction is to produce acrylonitrile complete oxidation
CO2, main reaction is：C3H3N(l)+9H2O(l)→3CO2(g)+HNO3+20H2(g), also the competition including water is anti-in electrolytic process
Should, react and be：H2O(l)→1/2O2(g)+H2(g)。
The mechanism of main reaction is：
Anode reaction：C3H3N(l)+9H2O(l)→3CO2(g)+NO3 -+21H+(l)+20e-
Cathode reaction：20H+(l)+20e-→10H2(g)
Completed cell is reacted：C3H3N(l)+9H2O(l)→3CO2(g)+HNO3+10H2(g)
Specifically,
The invention provides a kind of method for acrylonitrile of degrading, it is characterised in that comprises the following steps：
1) device that is used for acrylonitrile reduces of the structure as described in claim any one of 1-3, for acrylonitrile degraded
Device includes solar energy-thermo-electrically converting system, and solar energy optical and thermal-point converting system includes optical and thermal unit, opto-electronic element
And electrochemical cell, photo-thermal unit include being used for the solar energy stove for adjusting electrochemical cell temperature, photovoltaic element is multistage silicon substrate
Solar cell, electrochemical cell are electrolytic cell, and the anode in electrochemical cell uses Ti/ (IrO2&Ta2O5) electrode, negative electrode adopts
Use platinum electrode；
2) optical and thermal unit, opto-electronic element are adjusted, provides electric energy by opto-electronic element, optical and thermal unit provides height for reaction
Warm environment；
3) electrolytic process is carried out in undivided cell, control dc source electric current is constant in 50mA, reaction 0.5h-2h
To complete electrolysis, the electrolyte Na of electrolytic solution2SO4, pH=4~12, temperature be more than 50 DEG C.
Further, the electrolyte of the electrolytic solution is the Na that concentration is 3-10g/L2SO4, preferred concentration is 5g/L's
Na2SO4。
Further, the pH of the electrolytic solution is 3-7, and preferably pH is 3,4,5,6,7 or in-between arbitrary values.
Further, the temperature of the 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, preferably 50-100
DEG C, more preferably 85-95 DEG C, most preferably 90 DEG C.
Further, the time of electrolysis is 1-2h.
Present invention also offers a kind of experimental rig for being used to detect organic matter degradation, it is characterised in that including solar energy
Optical and thermal-power conversion system, the solar energy optical and thermal-point converting system include photo-thermal unit, photovoltaic element and electrochemical cell,
The light source of simulated solar, and analytical instrument, the photo-thermal unit include being used for the condenser lens for adjusting electrochemical cell temperature,
Photovoltaic element is photocell, and electrochemical cell is electrolytic cell.
Further, the organic matter is acrylonitrile.
Brief description of the drawings
The electrochemical experimental device figure of Fig. 1 laboratory tests
In figure：1- magnetic rotors；2- digital display heat-collecting magnetic stirring devices；3- negative electrodes；4- anodes；5- electrochemical workstations
The CGCM figure of Fig. 2 Solar uses
In figure：1- solar energy；2- light (one-level)；3- heat (two level)；4- electricity (two level)；5- is heated at high temperature；6- is pyrolyzed；7- light
Solution；8- photosensitizers；9- photocatalysis；10- electric fields；11- electrochemistry；12- pollutant water inlets；13- water delivery ports up to standard；14- is indulged
To coupling；15- transverse couplings
The circuit connection diagram of experimental provision outside Fig. 3 rooms
In figure：1- solar energy；2- delivery ports；3- water inlets；4- reactors；5- condensers；6- photovoltaic modulies
Fig. 4 Different electrodes degraded after acrylonitrile concentration with the reaction time change
Embodiment
Acrylonitrile simulates the preparation of sewage：
(1) appropriate acrylonitrile is measured, 1000mg/L storing solution is configured to water dissolving, is stored under the conditions of 4 DEG C, makes
Used time is diluted to required concentration.
(2) weigh appropriate sodium sulphate, be dissolved into 50g/L electrolyte storing solution with water, be diluted to during use needed for it is dense
Degree.The sodium sulfate concentration wherein used in example is 5g/L.
001 laboratory test research：
The indoor electrolysis unit of this experiment is as shown in figure 1, providing the temperature needed for electrolysis using in Fig. 12 and continuing to carry out
Stirring, while use homemade glass container to contain well mixed acrylonitrile electrolysis liquid as electrolytic cell.Experiment is using double electricity
Polar body system, negative electrode (3 in such as Fig. 1) use pure platinum electrode, and anode (4 in such as Fig. 1) uses Ti/ (IrO2&Ta2O5) electrode.Visit
Influence of each factor of rope to acrylonitrile solar energy STEP degradation effects, main thought are exactly the method using control unitary variant
To explore influence of each influence factor to acrylonitrile degradation effect.Thus solar energy STEP process oxidative degradations acrylonitrile is obtained most
Good process conditions.
Example 1：Anode uses Ti/ (IrO2&Ta2O5) electrode, negative electrode uses platinum electrode, with 6mA/cm2Current density,
Reaction time is 40min, and pH=3, reaction temperature is 50 DEG C, and concentration 200mg/L acrylic nitrile waste water is degraded, acrylonitrile
COD clearances are 48% after wastewater degradation.
Example 2：Anode uses Ti/ (IrO2&Ta2O5) electrode, negative electrode uses platinum electrode, with 6mA/cm2Current density,
Reaction time is 1h, and pH=7, reaction temperature is 50 DEG C, concentration 200mg/L acrylic nitrile waste water is degraded, acrylonitrile gives up
COD clearances are 47.1% after water degraded.
Example 3：Anode uses Ti/ (IrO2&Ta2O5) electrode, negative electrode uses platinum electrode, with 6mA/cm2Current density,
Reaction time is 1h, and pH=7, reaction temperature is 70 DEG C, concentration 200mg/L acrylic nitrile waste water is degraded, acrylonitrile gives up
COD clearances are 54.4% after water degraded.
Example 4：Anode uses Ti/ (IrO2&Ta2O5) electrode, negative electrode uses platinum electrode, with 6mA/cm2Current density,
Reaction time is respectively 2h, and pH=7, reaction temperature is 50 DEG C, and concentration 200mg/L acrylic nitrile waste water is degraded, propylene
COD clearances are 57.6% after nitrile wastewater degradation.
Example 5：Anode uses Ti/ (IrO2&Ta2O5) electrode, negative electrode uses platinum electrode, with 6mA/cm2Current density,
Reaction time is 1h, and pH=7, reaction temperature is 90 DEG C, concentration 200mg/L acrylic nitrile waste water is degraded, acrylonitrile gives up
COD clearances are 67% after water degraded.
Example 6：Anode uses graphite electrode, and negative electrode uses platinum electrode, with 6mA/cm2Current density, reaction time point
Not Wei 2h, pH=7, reaction temperature be 50 DEG C, concentration 100mg/L acrylic nitrile waste water is degraded, acrylic nitrile waste water degraded
Acrylonitrile clearance is 60.9% afterwards.
Example 7：Anode uses Ti/IrO2&Ta2O5Electrode, negative electrode uses platinum electrode, with 6mA/cm2Current density, instead
It is respectively 2h between seasonable, pH=7, reaction temperature is 50 DEG C, and concentration 100mg/L acrylic nitrile waste water is degraded, acrylonitrile
Acrylonitrile clearance is 67.5% after wastewater degradation.
Example 8：Anode uses Ti/RuO2&IrO2Electrode, negative electrode uses platinum electrode, with 6mA/cm2Current density, reaction
Time is respectively 2h, and pH=7, reaction temperature is 50 DEG C, concentration 100mg/L acrylic nitrile waste water is degraded, acrylonitrile gives up
Acrylonitrile clearance is 62.9% after water degraded.
Experiment 9：Anode uses Ti/SnO2&Sb2O3Electrode, negative electrode uses platinum electrode, with 6mA/cm2Current density, instead
It is respectively 2h between seasonable, pH=7, reaction temperature is 50 DEG C, and concentration 100mg/L acrylic nitrile waste water is degraded, acrylonitrile
Acrylonitrile clearance is 58.6% after wastewater degradation.
002 outdoor test is studied：
Outdoor location using STEP technology oxidation processes acrylic nitrile waste waters is as shown in Figure 3.Using too in optical and thermal unit
It is positive can stove (such as 5 in Fig. 3) come temperature needed for adjusting system response.Using single basic silicon based opto-electronicses pond in opto-electronic element
Unit, the conversion between solar energy and electric energy is realized, the electric energy for making to be converted to reaches electroaffinity necessary requirement, adjusts simultaneously
Focusing system (6 in such as Fig. 3), the matching between adjustment energy level/energy, spectrum, potential and efficiency.
Example 10：With Ti/ (IrO2&Ta2O5) electrode is anode, pure platinum electrode is negative electrode, and effective surface electrode product is
8cm2, pH=3, Na2SO4Electrolyte concentration is 5g/L, is the third of 100mg/L to concentration under conditions of being 90 DEG C in reaction temperature
Alkene nitrile waste water is handled, reaction time 30min, and COD clearances are 49.8% after acrylic nitrile waste water degraded.
Claims (8)
- A kind of 1. method for acrylonitrile of degrading, it is characterised in that comprise the following steps：1) device for acrylonitrile degraded is built, the device for acrylonitrile degraded includes solar energy-thermo-electrically conversion System, the solar energy-thermo-electrically converting system include optical and thermal unit, opto-electronic element and electrochemical cell, the optical and thermal Unit includes being used for the solar energy stove for adjusting electrochemical cell temperature, and opto-electronic element is multistage silica-based solar cell, electrification Unit is electrolytic cell；Anode in the electrochemical cell uses Ti/ (IrO2&Ta2O5) electrode, negative electrode uses platinum electrode；2) optical and thermal unit, opto-electronic element are adjusted, provides electric energy by opto-electronic element, optical and thermal unit provides high temperature ring for reaction Border；3) carry out electrolytic process in undivided cell, control dc source electric current is constant in 50mA, reaction 0.5h~2h with Complete electrolysis, the electrolyte Na of electrolytic solution2SO4Concentration be 5g/L, pH=4~12, temperature is more than 50 DEG C.
- 2. the method for degraded acrylonitrile according to claim 1, the pH of the electrolytic solution is 3~7.
- 3. the method for degraded acrylonitrile according to claim 2, it is characterised in that：The pH of the electrolytic solution is 3,4,5,6 or 7.
- 4. the method for the degraded acrylonitrile according to claim any one of 1-3, the temperature of the electrolytic solution for 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 More than and, or 90 DEG C and more than.
- 5. the method for degraded acrylonitrile according to claim 4, it is characterised in that：The temperature of the electrolytic solution is 50~100 DEG C.
- 6. the method for degraded acrylonitrile according to claim 5, it is characterised in that：The temperature of the electrolytic solution is 85~95 DEG C.
- 7. the method for degraded acrylonitrile according to claim 6, it is characterised in that：The temperature of the electrolytic solution is 90 DEG C.
- 8. the method for the degraded acrylonitrile according to claim any one of 1-2, the time of electrolysis is 1~2h.
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| CN108051387B (en) * | 2018-01-10 | 2020-01-21 | 东北石油大学 | Integrated in-situ solar thermal-electrochemical micro-analysis device |
| CN108275811B (en) * | 2018-01-10 | 2021-02-09 | 东北石油大学 | Method for degrading organic wastewater by solar energy through photo-electric-thermal three-field coupling |
| CN109160662A (en) * | 2018-10-15 | 2019-01-08 | 东北石油大学 | A kind of energy conservation and environmental protection oil field waste water treatment system and its method for handling oil field waste |
| CN109574343A (en) * | 2019-01-21 | 2019-04-05 | 东北石油大学 | The demulsification processing method of oily wastewater solar energy STEP |
| CN109671512A (en) * | 2019-01-22 | 2019-04-23 | 东华理工大学 | A kind of electrochemistry and photo-thermal evaporation process nuclear waste water device based on solar energy |
| CN113789018B (en) * | 2021-01-28 | 2024-06-04 | 海信容声(广东)冰箱有限公司 | SAN material for refrigerator transparent piece, preparation method of SAN material and refrigerator transparent piece |
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