CN106731542A - The apparatus for electrochemical treatment and method of a kind of phosphine gas - Google Patents
The apparatus for electrochemical treatment and method of a kind of phosphine gas Download PDFInfo
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- CN106731542A CN106731542A CN201611218299.3A CN201611218299A CN106731542A CN 106731542 A CN106731542 A CN 106731542A CN 201611218299 A CN201611218299 A CN 201611218299A CN 106731542 A CN106731542 A CN 106731542A
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- gas
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- hydrogen phosphide
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 121
- 238000009792 diffusion process Methods 0.000 claims abstract description 62
- 238000010521 absorption reaction Methods 0.000 claims abstract description 41
- 239000003792 electrolyte Substances 0.000 claims abstract description 39
- 230000005518 electrochemistry Effects 0.000 claims abstract description 34
- 238000005276 aerator Methods 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 14
- 239000011229 interlayer Substances 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004745 nonwoven fabric Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 2
- 238000003487 electrochemical reaction Methods 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 230000008859 change Effects 0.000 description 9
- 239000002912 waste gas Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 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
- ROJYSBSWRTYOFQ-UHFFFAOYSA-N N#CC#N.[S].[P] Chemical compound N#CC#N.[S].[P] ROJYSBSWRTYOFQ-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
- B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
Landscapes
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses the apparatus for electrochemical treatment and method of a kind of phosphine gas, device includes reative cell, also includes：At least one of which gas diffusion anode of the level in the reative cell, the lower section of bottom gas diffusion anode is gas pressurized room, top is electrochemistry absorption chamber；Mesh cathode and aerator in the electrochemistry absorption chamber, the mesh cathode pass through wire external power supply with gas diffusion anode；And the air inlet on the gas pressurized room, gas pressurized equipment is set on the external pipeline of the air inlet.By pressurizeing, be pressed into hydrogen phosphide tail gas in gas pressurized room by air pump, through gas diffusion anode, phosphate is oxidized at anode/electrolyte interface, remaining hydrogen phosphide is dissolved in electrolyte, further it is oxidized into the hydrogen phosphide in electrolyte, realizes that hydrogen phosphide fully absorbs degraded.
Description
Technical field
The present invention relates to a kind of processing method of phosphine gas, belong to technical field of waste gas treatment.
Background technology
Hydrogen phosphide (PH3) it is a kind of colourless, hypertoxic, inflammable gas, occur mainly with grain depot fumigant insect killing, secondary phosphorus
During sour sodium production, semi-conductor industry, phosphorus production and sludge settling etc..Because phosphine gas have severe toxicity, when its
Concentration is 2~4mg/m in air3When, people can smell its smell；When its in atmosphere concentration be more than 9.7mg/m3When, people can be caused
Poisoning；When its in atmosphere concentration be 550~830mg/m3When, death can occur in 0.5~1.0 hour after people's contact；
When its in atmosphere concentration more than 2798mg/m3When, can make one rapid lethal.In order to prevent the gaseous mixture containing phosphine gas
Phosphine gas must be processed by pollution and biological murder by poisoning of the body to environment before discharge.
Phosphine waste gas are carried out in currently available technology the apparatus and method of absorption cleaning mainly have combustion method, wet method and
Dry method.Wherein combustion method is traditional hydrogen phosphide processing method, and generation of being burnt in incinerator is blended in by hydrogen phosphide and air
Phosphoric acid smog, gained smog is passed through the phosphoric acid that absorption tower is obtained technical grade, but the shortcoming of the method is that incinerator is added using electricity
Heat, belongs to high-energy equipment, and the phosphoric acid smog of generation has stronger corrosivity, and each section of temperature difference of incinerator to reactor
Greatly, it is unfavorable for safety in production, also there is gas leakage.Wet-treating hydrogen phosphide is that to use sodium hypochlorite be absorbent, raw
Into relatively stable phosphoric acid salt, have the disadvantage：Produce the accessory substance chlorine of big quantitative response to cause secondary pollution, it is hypochlorous chemically
Matter is unstable, is extremely easy in decomposition, fails, it is necessary to frequently change absorbing liquid, increases extra cost.Dry process hydrogen phosphide is using work
Property charcoal hydrogen phosphide is adsorbed, but without change hydrogen phosphide chemical property, weak point be absorption after activated carbon to adopt
With or burning or parsing method carry out later stage treatment, however it remains pollution problem.
Above method either chemical transfer method and absorption method, mostly more or less causes a certain degree of secondary dirt
Dye.
The Chinese invention application documents of publication number CN 103551031A disclose a kind of electrochemistry collaboration liquid-phase catalysis
The method and device of oxidation, purification phosphorus sulphur cyanogen, by electrochemical oxidation, catalyst aoxidize collective effect by phosphorous, sulphur,
One or more in cyanogen of gaseous mixture is processed, and phosphorus, sulphur, cyanogen are oxidized to phosphoric acid, elemental sulfur, titanium dioxide respectively after treatment
Carbon and nitrogen or ammonia, but need to add heavy metal in the absorption of the method, can not only increase cost, absorb waste liquid difficulty
Reason.Assimilation effect only is difficult to ensure that by once absorbing, and anode electrode produces oxygen limited, is only applicable the gas of low concentration.
The content of the invention
Part, of the invention to propose a kind of electrochemical process for treating of phosphine gas in view of the shortcomings of the prior art, adopts
With the inventive method and it is aided with corresponding equipment i.e. present device so that the phosphine waste gas of discharge fully absorb degraded,
Realize that hydrogen phosphide " zero " content is discharged, while avoiding a large amount of chemical oxidizing agents needed for traditional chemical absorption process, it is to avoid
Secondary pollution.
A kind of apparatus for electrochemical treatment of phosphine gas, including reative cell, also include：
At least one of which gas diffusion anode of the level in the reative cell, the lower section of bottom gas diffusion anode is gas
Body compression chamber, top are electrochemistry absorption chamber；
Mesh cathode and aerator in the electrochemistry absorption chamber, the mesh cathode and gas diffusion anode
By wire external power supply；
And the air inlet on the gas pressurized room, gas pressurized is set on the external pipeline of the air inlet and is set
It is standby.
In parallel between multi-layer gas diffusion anodes, the pressurized equipment can add using force (forcing) pump or booster fan etc. are conventional
Pressure equipment, in hydrogen phosphide electrochemistry absorption chamber, phosphine containing waste gas is pumped into the present invention by gas pressurized, is expanded through gas
Anode is dissipated, most of hydrogen phosphide is oxidized to phosphate, remains under the effect of additional power source positive potential at anode/electrolyte interface
Remaining hydrogen phosphide dissolves in electrolyte；Air, the matter that oxygen components are transmitted under the effect of negative electrode negative potential with anode are passed through in electrolyte
Son is combined and is reduced into hydrogen peroxide, so that further oxidation retention is dissolved in the remaining phosphine gas in electrolyte, so as to realize phosphorus
Change hydrogen and fully absorb degraded.
Anode/electrolyte interface occur specific reaction equation be：
(1)PH3+4H2O→PO4 3-+11H++8e-
Cathode electrode occur specific reaction equation be：
(2)O2+2H2O+2e-→H2O2+2OH-
(3)H2O2+PH3+2OH-→HPO3 2-+5H2O。
Isolated by gas diffusion anode and corresponding backing material between the gas pressurized room and electrochemistry absorption chamber；
Gas diffusion anode electrode can make phosphine gas freely be passed through hydrogen phosphide electrochemistry absorption chamber, while phosphatization can be prevented
Electrolyte permeability in hydrogen electrochemistry absorption chamber.
Preferably, the gas diffusion anode is rolled over being prepared from reticulated metallic material by carbon black and activated carbon, living
Property charcoal and carbon black ratio be 1:2~1:5, the thickness of gas diffusion anode is 0.5mm~2mm.
Further preferably, activated carbon and carbon black ratio are 1:2~3；Still more preferably it is 1:2, suitable ratio can
Hydrogen phosphide in efficient oxidative absorption waste gas, while the excellent gas permeability of diffusion anodes electrode can be kept.
By taking best proportion as an example, specific operating method is as follows：Take activated carbon 10g and carbon black 20g is dissolved in ethanol solution
In (300mL), be sufficiently stirred for adding polytetrafluoroethylene (PTFE) 60g after 1h, be stirred for 1h, then at 80 DEG C heating evaporation ethanol to dough
Shape, it is the anode electrode of 1mm doughy mixture to be compressed on stainless (steel) wire by roll squeezer then thickness is obtained, finally
Gas diffusion anode is obtained after being calcined 20 minutes at 340 DEG C.
The preparation of gas diffusion anode can be realized using prior art in itself, the sun for simply being prepared under above-mentioned preparation method
Polarity can be more preferably.
Preferably, it is 1~5 layer, the spacing between adjacent gas diffusion anodes that the gas diffusion anode is set to the number of plies
It is 5cm~30cm.Multilayer diffusion anodes electrode of the present invention can disperse to the gas of phosphine containing.Waste gas is divided
Some small and weak air-flows are dissipated into, the contact area of gas-liquid is increased, reaction probabilities is increased so that hydrogen phosphide is in anode/electrolyte
Interface can be fully absorbed.The gas that the anode adaptation various concentrations that the different numbers of plies can also be utilized are set of multi-layered anode.
It is further preferred that the gas diffusion anode is set to the number of plies for 3~5 layers, between adjacent gas diffusion anodes
Spacing be 10cm~20cm, the thickness of mono layer gas diffusion anodes is 0.8~1.2mm.
It is further preferred that the gas diffusion anode is set to the number of plies for 5 layers, between adjacent gas diffusion anodes
Spacing is 20cm, and the thickness of mono layer gas diffusion anodes is 1mm.
It is further preferred that being additionally provided with the support frame for support substrate gas diffusion anode.
Preferably, interlayer is provided with the electrochemical reaction room and between gas diffusion anode and mesh cathode, institute
Aerator is stated to be located between the interlayer and mesh cathode.Further preferably, the interlayer is non-woven fabrics.
Interlayer is located between cathode electrode and anode electrode, and interlayer material is non-woven fabrics, it is ensured that air will not spread
To anode, so as to avoid the absorbent properties of the hydrogen phosphide for influenceing anode, while its is cheap, hydrogen phosphide can also be disperseed, carried
The absorption efficiency of negative electrode high.
Further, the aerator is micro-hole aerator, and aeration mode is micropore gas explosion.The profit of air can be increased
With rate, the hydrogen peroxide yield of negative electrode is improved.
Preferably, the mesh cathode is nickel screen, titanium net or stainless (steel) wire, and mesh number is 100-150 mesh；More preferably
The stainless (steel) wire of 100-150 mesh；The most preferably stainless (steel) wire of 150 mesh.Further, in the mesh cathode covering reative cell
Whole cross section.Generation hydrogen peroxide efficiently can be combined with proton using the oxygen components in air, and stainless (steel) wire is made
Valency is cheap, can be magnified in actual applications utilization with excellent conductive performance.
Preferably, the reative cell top is provided with hydrogen phosphide detector.For in tail gas after detection process hydrogen phosphide it is dense
Degree.
Further, the top of the electrolyte being arranged in the electrochemistry absorption chamber.
The ratio of height to diameter of the electrochemistry absorption chamber reactor is 1:1~5:1.Further preferably, the Gao Jing of the reactor
Than being 2~3:1, most preferably 3:1.
Preferably, the gas pressurized room and hydrogen phosphide electrochemistry absorption chamber are arranged from the bottom up successively, and the gas adds
The volume ratio of pressure chamber and hydrogen phosphide electrochemistry absorption chamber is 1:1~1:10；Further preferably, gas pressurized room and hydrogen phosphide electrification
The volume ratio for learning absorption chamber is 1:1~1:5；Most preferably 1:5.
The present invention also provides a kind of method that hydrogen phosphide tail gas absorption is carried out using the apparatus for electrochemical treatment, including such as
Lower step：
(1) hydrogen phosphide tail gas is pressed into gas pressurized room by the air pump that pressurizes, air pressure is 0.5MPa-1.5MPa.
(2) hydrogen phosphide tail gas passes through gas diffusion anode, and phosphate, phosphoric residue are oxidized at anode/electrolyte interface
Change hydrogen is dissolved in electrolyte；
(3) air is passed through in electrolyte, oxygen components are transmitted under the effect of mesh cathode negative potential with gas diffusion anode
Proton combine and be reduced into hydrogen peroxide so that further oxidation retention is dissolved in remaining phosphine gas in electrolyte, realize phosphorus
Change hydrogen and fully absorb degraded.
Preferably, the anodic current density of electrochemistry absorption chamber is in 100A/m2–300A/m2；Electricity in electrochemistry absorption chamber
Solution liquid is potassium hydroxide or NaOH, and concentration of electrolyte is 1mol/L-5mol/L.
Suitable current density ensure that effective oxidation hydrogen phosphide；While suitable basicity ensure that electrolyte
The absorption of hydrogen phosphide can be promoted.
It is further preferred that the anodic current density of electrochemistry absorption chamber is in 150A/m2–250A/m2；Electrochemistry absorbs
Electrolyte is potassium hydroxide solution in room, and concentration is 2mol/L-4mol/L.
It is further preferred that the anodic current density of electrochemistry absorption chamber is in 180A/m2–220A/m2；Electrochemistry is inhaled
Electrolyte is potassium hydroxide solution in receiving room, and concentration is 2.5mol/L-3.5mol/L.
Most preferably, the anodic current density of electrochemistry absorption chamber is in 200A/m2；Electrolyte is in electrochemistry absorption chamber
Potassium hydroxide solution, concentration is 3mol/L.
Gaseous hydrogen phosphide is converted to the phosphorus of liquid using the electrochemical oxidation hydrogen phosphide of multilayer diffusion anodes for the present invention
Hydrochlorate, non-secondary pollution is one efficient, to all inventions with positive effect of protection health and atmospheric environment.
Compared with prior art, beneficial effects of the present invention：
(1) it is an advantage of the invention that realizing fully absorbing for phosphine waste gas, and secondary pollution will not be produced.
(2) present invention is applied widely, goes for the phosphine gas of different scales various concentrations；Side of the invention
Method is applied to concentration in the treatment of the hydrogen phosphide tail gas of 0ppm~20000ppm, can reach the purpose for fully absorbing.
(3) apparatus of the present invention can realize that mechano-electronicization is operated by controlling power supply to change anodic current density, reduce
Person works' intensity, improve the security protection to personnel, and effectively, simple possible can engineering for whole device and process safety
Amplify, thoroughly solve hydrogen phosphide and absorb problem.
(4) without any chemical reagent, anode can ensure assimilation effect, it is possible to use the anode of the different numbers of plies can be with
The gas of various concentrations is adapted to, negative electrode generation hydrogen peroxide can ensure assimilation effect.
(5) gas of the invention absorbs and occurs in anode electrode/electrolyte interface, can fast and effectively absorb, except this
Outside, the hydrogen peroxide that negative electrode is produced can absorb the phosphine gas of the low concentration of remnants, it is ensured that gas is fully absorbed.
Brief description of the drawings
Fig. 1 is the structural representation of apparatus of the present invention.
Reference is as follows shown in figure：
1- gas pressurizeds room 2- support frame 3- electrochemistry absorption chambers
4- interlayer 5- aerator 6- hydrogen phosphide detectors
7- mesh cathode 8- power supply 9- gas diffusion anodes
10- gas feeds.
Specific embodiment
As shown in figure 1, a kind of apparatus for electrochemical treatment of phosphine gas, including reative cell, expanded by gas in reative cell
Dissipate anode 9 and corresponding support frame 2 is divided into upper and lower two reaction chambers, the space below gas diffusion anode adds for gas
Pressure chamber 1, gas pressurized room carries air inlet 10, and force (forcing) pump (not shown) is set on the external pipeline of air inlet 10, is located at
Space above gas diffusion anode is that electrolyte is contained in electrochemistry absorption chamber 3, electrochemistry absorption chamber, liquid level of electrolyte top
Hydrogen phosphide detector 6 is set.
Gas diffusion anode 6 is set to 1~5 layer, in parallel between all gas diffusion anodes, and support frame 2 is used to support bottom
Spacing between layer anode adjacent anode is 5cm~30cm, is further preferably set to 15cm~25cm；The thickness of single layer anode
It is 0.5mm~2mm, is further preferably set to 0.8~1.2mm.In present embodiment, most preferably it is set to：Gas diffusion
Anode is set to the number of plies for 3 layers, and the spacing between adjacent gas diffusion anodes is 20cm, and the thickness of mono layer gas diffusion anodes is
1mm。
Horizontally disposed mesh cathode 7 is additionally provided with electrochemistry absorption chamber, mesh cathode can use nickel screen, titanium net or stainless
Steel mesh, mesh number is 100-150 mesh；The stainless (steel) wire of 100~150 mesh, mesh cathode covering reaction are preferably in present embodiment
The whole cross section of room.
By the both positive and negative polarity of wire connecting power 8 between gas diffusion anode 9 and mesh cathode 7, in electrochemistry absorption chamber
And interlayer 4 is set between mesh cathode and gas diffusion anode, in present embodiment, interlayer is non-woven fabrics, aerator 5
It is arranged between interlayer and mesh cathode, prevents air from entering anode electrode, in present embodiment, aerator is exposed using micropore
Gas device.
In present embodiment, gas diffusion anode is prepared by the following method：
Take activated carbon 10g and carbon black 20g to be dissolved in ethanol solution (300mL), polytetrafluoroethylene (PTFE) is added after being sufficiently stirred for 1h
60g, is stirred for 1h, then at 80 DEG C heating evaporation ethanol to dough, then by roll squeezer by doughy mixture pressure
It is the anode electrode of 1mm to make and thickness is obtained on stainless (steel) wire, and gas diffusion sun is obtained after finally being calcined 20 minutes at 340 DEG C
Pole.
The method for carrying out hydrogen phosphide vent gas treatment using said apparatus is as follows：
(1) hydrogen phosphide tail gas is pressed into gas pressurized room by the air pump that pressurizes, air pressure is 0.5MPa-1.5MPa.
(2) hydrogen phosphide tail gas passes through gas diffusion anode, and phosphate, phosphoric residue are oxidized at anode/electrolyte interface
Change hydrogen is dissolved in electrolyte；
(3) air is passed through in electrolyte, oxygen components are transmitted under the effect of mesh cathode negative potential with gas diffusion anode
Proton combine and be reduced into hydrogen peroxide so that further oxidation retention is dissolved in remaining phosphine gas in electrolyte, realize phosphorus
Change hydrogen and fully absorb degraded.
Contain electrolyte in electrochemistry absorption chamber, electrolyte use sodium hydroxide solution or potassium hydroxide solution concentration for
2mol/L-4mol/L；The anodic current density of electrochemistry absorption chamber is in 150A/m2–250A/m2。
Embodiment 1
Electrochemistry absorber：Diameter 50cm, 150cm high, (activated carbon is 1 with carbon black ratio to anode electrode:2) the electrode number of plies
It it is 3 layers, electrode spacing is 10cm, and every layer of thickness of electrode is 0.5mm, and cathode electrode is the stainless (steel) wire of 100 mesh.Electrolyte is
The sodium hydroxide solution of 1mol/L.Turn on the power, it is 100A/m to control anodic current density2, open air aeration device and tail
Gas force (forcing) pump.Hydrogen phosphide tail gas (1000ppm) passes through multilayer diffusion anodes electrode successively after being pressed into gas diffusion chamber (1.0MPa),
Phosphate is oxidized at each layer of anode/electrolyte interface, while cathode electrode annex produces substantial amounts of hydrogen peroxide, hydrogen peroxide
With by hydrogen phosphide remaining after anode electrode and non-woven fabrics diffusion, by chemical absorbing, the hydrogen phosphide detector of top shows reading
It is 0ppm.Phosphine waste gas realize the removal completely of hydrogen phosphide by the common left and right of multilayer diffusion anodes and hydrogen peroxide.
Embodiment 2
Electrochemistry absorber：Diameter 30cm, 100cm high, (activated carbon is 1 with carbon black ratio to anode electrode:4) the electrode number of plies
It it is 5 layers, electrode spacing is 20cm, and every layer of thickness of electrode is 1mm, and cathode electrode is the stainless (steel) wire of 160 mesh.Electrolyte is
The sodium hydroxide solution of 3mol/L.Turn on the power, it is 200A/m to control anodic current density2, open air aeration device and tail
Gas force (forcing) pump.Hydrogen phosphide tail gas (20000ppm) passes through multilayer diffusion anodes electricity successively after being pressed into gas diffusion chamber (0.5MPa)
Pole, phosphate is oxidized at each layer of anode/electrolyte interface, while cathode electrode annex produces substantial amounts of hydrogen peroxide, it is double
Oxygen water is with by hydrogen phosphide remaining after anode electrode and non-woven fabrics diffusion, by chemical absorbing, the hydrogen phosphide detector of top shows
Reading is 0ppm.Phosphine waste gas realize the removal completely of hydrogen phosphide by the common left and right of multilayer diffusion anodes and hydrogen peroxide.
The specific implementation case of patent of the present invention is the foregoing is only, but the technical characteristic of patent of the present invention is not limited to
This, any those skilled in the relevant art in the field of the invention, all cover of the invention special by the change or modification made
Among sharp scope.
Claims (10)
1. a kind of apparatus for electrochemical treatment of phosphine gas, including reative cell, it is characterised in that also include：
At least one of which gas diffusion anode of the level in the reative cell, the lower section of bottom gas diffusion anode adds for gas
Pressure chamber, top are electrochemistry absorption chamber；
Mesh cathode and aerator in the electrochemistry absorption chamber, the mesh cathode pass through with gas diffusion anode
Wire external power supply；
And the air inlet on the gas pressurized room, gas pressurized equipment is set on the external pipeline of the air inlet.
2. apparatus for electrochemical treatment according to claim 1, it is characterised in that in the electrochemical reaction room and positioned at gas
Interlayer is provided between diffusion anodes and mesh cathode, the aerator is located between the interlayer and mesh cathode.
3. apparatus for electrochemical treatment according to claim 2, it is characterised in that the interlayer is non-woven fabrics.
4. apparatus for electrochemical treatment according to claim 1, it is characterised in that it is 1 that the gas diffusion anode sets the number of plies
~5 layers, the spacing between adjacent gas diffusion anodes is 5cm~30cm.
5. apparatus for electrochemical treatment according to claim 4, it is characterised in that be additionally provided with for support substrate gas diffusion sun
The support frame of pole.
6. apparatus for electrochemical treatment according to claim 1, it is characterised in that the gas diffusion anode is by carbon black and activity
Charcoal is rolled over being prepared from reticulated metallic material, and the ratio of activated carbon and carbon black is 1:2~1:5, the thickness of gas diffusion anode
It is 0.5mm~2mm to spend.
7. apparatus for electrochemical treatment according to claim 1, it is characterised in that the mesh cathode is nickel screen, titanium net or not
Rust steel mesh, mesh number is 100-150 mesh.
8. apparatus for electrochemical treatment according to claim 1, it is characterised in that the reative cell top is provided with hydrogen phosphide detection
Device.
9. it is a kind of to carry out hydrogen phosphide tail gas absorption using apparatus for electrochemical treatment described in claim 1~8 any claim
Method, it is characterised in that comprise the following steps：
(1) hydrogen phosphide tail gas is pressed into gas pressurized room by the air pump that pressurizes, air pressure is 0.5MPa-1.5MPa.
(2) hydrogen phosphide tail gas passes through gas diffusion anode, and phosphate, remaining hydrogen phosphide are oxidized at anode/electrolyte interface
In dissolving in electrolyte；
(3) air, the matter that oxygen components are transmitted under the effect of mesh cathode negative potential with gas diffusion anode are passed through in electrolyte
Son is combined and is reduced into hydrogen peroxide, so that further oxidation retention is dissolved in the remaining phosphine gas in electrolyte, realizes hydrogen phosphide
Fully absorb degraded.
10. method according to claim 9, it is characterised in that the anodic current density of electrochemistry absorption chamber is in 100A/m2–
300A/m2；Electrolyte is potassium hydroxide or NaOH in electrochemistry absorption chamber, and concentration of electrolyte is 1mol/L-5mol/L.
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