CN104445533B - A kind of ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor - Google Patents
A kind of ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 88
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- 239000007788 liquid Substances 0.000 claims abstract description 24
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 10
- 239000010802 sludge Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 238000005422 blasting Methods 0.000 claims description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001952 rubidium oxide Inorganic materials 0.000 claims description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000010790 dilution Methods 0.000 abstract 1
- 239000012895 dilution Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000003851 biochemical process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention provides a kind of ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor, this inside reactor comprises photoelectrocatalysioxidization oxidization reactive system and ring-type spoke stream negative pressure suction type internal recycle water inlet system, wherein photoelectrocatalysioxidization oxidization reactive system comprises board-like tubular DSA anode and net formula tubular Ti cathode, fill granular photoelectric between anode and cathode, net formula tubular Ti cathode inside arranges ultraviolet producer.Photoelectrocatalysioxidization oxidization reactive system bottom arranges ring-type spoke stream negative pressure suction type internal recycle water inlet system, water inlet system center arranges spouting of liquid pipe, the venturi place of spouting of liquid pipe arranges some length adjustable pipelines, is connected by the ring-type radial-flow water inlet device of spouting of liquid pipe with the densely covered isometrical circular hole being positioned at reactor bottom region.Reactor head arranges gas injection tube, and gas injection tube inlet mouth is connected with air driven pump, and air outlet is connected with air, and venturi place is connected with reactor head vapor pipe, and the hydrogen that inside reactor produces is put in dilution side by side.
Description
Technical field
The invention belongs to Industrial Wastewater Treatment professional domain, be specifically related to a kind of internal recycle photoelectrocatalysis reaction unit for the treatment of high salt organic wastewater with difficult degradation thereby.
Background technology
In recent years, along with National Industrial and expanding economy, the continuous entered environment of many waste water containing being difficult to biodegradable hazardous and noxious substances, to know clearly very large harm to industrial and agricultural production, people's lives and HUMAN HEALTH band, under this background, the standard of national requirements discharge of wastewater is more and more stricter, the difficulties be treated as in field of Environment Protection up to standard of many used water difficult to degradate.
And on the other hand, photoelectro-catalytic oxidation technology as a kind of brand-new high-level oxidation technology successful Application in high-salt wastewater treatment industry, photo-electrocatalytic technology is the novel advanced oxidation processes of a kind of photochemical catalysis and electrocatalysis combined utilization, mainly by applying bias-voltage on the working electrode (s, thus form a potential gradient at electrode and catalytic inner, promote that light induced electron and hole are moved in the opposite direction, suppress their compound, to accelerate to be separated.And, this photoelectro catalytic system also has two other outstanding advantage, one is that the reduction process of conduction band electron is separated (compared with semiconductive particles) with the oxidising process of valence band hole from locus, and result considerably increases the formation efficiency of semiconductor surface OH and restoring of preventing intermediate oxidation product on negative electrode; Two is the H be introduced to due to conduction band electron in cathodic reduction water
+, so do not need to blast oxygen as electron capture agent to system.But photoelectro-catalytic oxidation technology is when degradable organic pollutant at present, because the number of free radical produced is minimum, so there is the shortcomings such as reaction efficiency is low, the treatment time is long, therefore, how to promote the processing efficiency of photoelectro-catalytic oxidation technology, reducing ton water treatment energy consumption, is the research emphasis in this technical field current and difficult point.The internal recycle photoelectrocatalysioxidization oxidization reactor developed for the short slab problem of photoelectro-catalytic oxidation technology generally adopts traditional gas blower aeration method to realize, the method by blasting air in the water body of reactor bottom region, form certain negative pressure state at reactor bottom, thus reach the internal recycle state of waste water at inside reactor.Under same current density condition being caused when but gas content increases in the waste water between cathode-anode plate, bath voltage between anode and cathode raises greatly, therefore ton water treatment power consumption also can correspondingly increase, and mass-transfer progress also can reduce UV-light in water body by property, greatly reduce the effect of photoelectrocatalysioxidization oxidization process waste water.Therefore, according to the relevant inner circulation reactor of traditional aeration type internal recycle theory exploitation, no matter be in treatment effect or in ton water consumption, all can not reach the design effect of internal recycle photoelectrocatalysioxidization oxidization reactor, for the above drawback of the internal recycle photoelectrocatalysioxidization oxidization reactor of traditional aeration type type, be necessary to redesign and exploitation, under reaching the condition that treatment effect remains unchanged, the reduction greatly of ton water consumption.
Summary of the invention
The object of the invention is to design a kind of ring-type spoke stream negative pressure suction type internal recycle photoelectrocatalysioxidization oxidization reactor, in order to solve the difficult problem that traditional aeration type internal recycle photoelectrocatalysioxidization oxidization reactor for treatment efficiency is low, energy consumption is large.
For realizing above-mentioned technical problem, the invention provides a kind of ring-type spoke stream negative pressure suction type internal recycle photoelectrocatalysioxidization oxidization reactor, it is characterized in that, described reactor head is provided with gas injection tube, the inlet mouth of described gas injection tube is connected with air driven pump, and the venturi of gas injection tube is connected with reactor head vapor pipe; The air outlet of gas injection tube and air lead directly to, and by blasting pressurized air with pressure in gas injection tube, near gas injection tube venturi, form negative pressure, and the hydrogen that suction inside reactor produces also dilutes, and is then discharged in air by vapor pipe;
Described inside reactor mainly comprises photoelectrocatalysioxidization oxidization reactive system and the ring-type spoke stream negative pressure suction type internal recycle water inlet system be connected; The bottom of described reactor is provided with the reactor water inlet pipe arranged bottom sludge hopper and sludge hopper; Described reactor water inlet pipe is connected with the spouting of liquid pipe of described ring-type spoke stream negative pressure suction type internal recycle water inlet system, throw out periodic exhaustion in sludge hopper;
Described ring-type spoke stream negative pressure suction type internal recycle water inlet system comprises the spouting of liquid pipe in the middle of water inlet system, bottom described spouting of liquid pipe, water-in is connected with reactor water inlet pipe, in the middle of spouting of liquid pipe, venturi place has some length adjustable pipelines to be connected with the ring-type radial-flow water inlet device of the densely covered isometrical circular hole being positioned at reactor bottom region, by controlling the length of length adjustable pipeline, ring-type radial-flow water inlet device water inlet device can be regulated in the position of inside reactor; Spouting of liquid pipe top is connected with a taper type water distributor, gather isometrical water distributing pore at described taper type water distributor top, in order to the even waste water entered from spouting of liquid pipe, and described taper type water distributor top is connected with the back up pad being densely covered with isometrical circular hole, described back up pad is used for support photoelectrocatalysioxidization oxidization reactive system and stationary ring spoke stream negative pressure suction type internal recycle water inlet system;
Described photoelectrocatalysioxidization oxidization reactive system comprises setting one piece of board-like tubular DSA anode on the supporting plate and one piece of net formula tubular Ti cathode, cathode-anode plate spacing is preferably 0.5-2cm, be filled with granular photoelectric between cathode-anode plate, net formula tubular Ti cathode inside is provided with ultraviolet producer;
Wherein said water distributing pore diameter is less than described granular photoelectrocatalysis oxidant layer bottom minimum grain size;
First the waste water entered by spouting of liquid pipe in ring-type spoke stream negative pressure suction type internal recycle water inlet system can enter between the anode and cathode of photoelectrocatalysioxidization oxidization system, after photoelectrocatalysioxidization oxidization process, carry out repeatedly circular treatment by internal circulation system again, circulation ratio determines by flow velocity when entering reactor.
According to ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor of the present invention, wherein said back up pad is preferably provided with a hollow cathode board groove and a circular anode board groove, annular slot diameter equals corresponding tubular pole plate diameter, and back up pad diameter equals reactor inside diameter; Diameter that described ring-type radial-flow water inlet device gathers is less than the circular hole of 0.3cm, and ring-type radial-flow water inlet device diameter is preferably the 0.5-0.8 of reactor inside diameter doubly.
According to ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor of the present invention, wherein said reactor is cylindrical, and wall internal layer material is the corrosion resistant material such as hard PVC, PPR, and outer material is stainless steel.
According to ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor of the present invention, wherein said board-like tubular DSA positive plate is the precious metal anode plate that titanium substrate surface supported noble metals material is prepared from, and precious metals species adopts one or more materials in platinum, ruthenium, iridium, rubidium and Zirconium oxide to form; Described board-like tubular DSA anode and described net formula tubular Ti cathode polar plate spacing are preferably 0.5-2cm.
According to ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor of the present invention, the granular photoelectric of wherein said inside reactor adopt in Alpha-alumina or silicon-dioxide one or more be carrier, one or more active substances in surface load titanium dioxide, Cadmium Sulfide, ferric oxide, Manganse Dioxide are formed, and there is cracking and open loop function, and pore structure tunable characteristic, be prepared into honeycomb vesicular structure.
According to ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor of the present invention, wherein described photoelectric layering is filled between cathode-anode plate, wherein bottom and top layer photoelectric median size maximum, particle diameter is at 0.3cm ~ 0.5cm; Middle layer catalyzer median size is minimum, and particle diameter is at 0.1cm ~ 0.3cm, and the dosage of described granular photoelectric is 1:200-1:20 with the mass ratio of waste water in reaction; Described water distributing pore diameter R < 0.3cm.
According to ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor of the present invention, one in the high voltage mercury lamp of wherein said inside reactor photoelectrocatalysioxidization oxidization system medium ultraviolet producer to be wavelength be 200-400nm, medium pressure mercury lamp and ultraviolet lamp, power is 4-200W;
According to ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor of the present invention, wherein said ultraviolet producer profile is cylindrical, and its external diameter equals netted cartridge type titanium negative plate internal diameter.
According to ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor of the present invention, wherein said gas injection tube air outlet is directly connected with air, by blasting the pressurized air that pressure is 0.2-1Mpa, negative pressure state is formed at gas injection tube venturi place, the hydrogen sucking-off that inside reactor is produced also is diluted to concentration less than 4%, finally enters air.
Reactor principle of work of the present invention is according to Bernoulli Jacob's jet gravitation principle, when waste water with high flow rate from reactor bottom water inlet pipe through spouting of liquid pipe venturi, subnormal ambient can be formed at venturi place, at this moment the waste water in reactor bottom region will enter connecting tube by radial-flow ring-type water inlet device, and then enter to be formed in region between photoelectrocatalysioxidization oxidization reactive system anode and cathode by spouting of liquid pipe venturi and circulate, this part waste water mixes with the waste water entered from water-in thus improves the solution total amount of circulation, the flow rate ratio of 2:1 ~ 5:1 can be produced by ring-type spoke stream negative pressure suction type internal recycle water inlet system, its effect is consistent with traditional aeration type internal recycle effect, but due to entering without any gas, under the condition of identical current density, the increase of bath voltage between anode and cathode can not be caused, also the perviousness of UV-light in waste water can not be caused, therefore the treatment effect of reactor can not be reduced, and greatly reduce ton water treatment energy consumption.And can prove by experiment, in large-scale solution tank, annular arrangement is placed with higher mixing efficiency than single, therefore the radial-flow ring-type water inlet device of the isometrical circular hole that gathers is adopted, promote water inlet efficiency, and radial-flow annular water inlet device should be placed in container bottom as much as possible to reach maximum flow rate.
The present invention relates to ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor to compare with legacy equipment, there is following beneficial effect:
1, do not need to inside reactor aeration, under the condition of same current density, greatly can reduce the bath voltage between anode and cathode, thus greatly reduce ton water treatment energy consumption.
2, do not need to inside reactor aeration, can avoid being deteriorated because gas is dissolved in the UV light permeability caused in waste water, thus keep the effect of photoelectrocatalysioxidization oxidization constant.
3, do not need, to inside reactor aeration, the working cost of aerator can be reduced, thus reduce the process energy consumption of ton water further overall operation condition.
Accompanying drawing explanation
Accompanying drawing 1 is ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor structural representation;
Accompanying drawing 2 is ring-type spoke stream negative pressure suction type internal recycle water inlet system structure iron;
Wherein, in figure
1 be sludge hopper 11 is board-like tubular DSA positive plate
2 is ring-type spoke stream negative pressure suction type internal recycle water inlet 12 for reactor water inlet pipe system 13 is back up pad
3 be photoelectric 14 is length adjustable connecting tube
4 be ultraviolet producer 15 is spouting of liquid pipe venturi
5 be reactor water port 16 is spouting of liquid pipe
6 is gas injection tube 17 is radial-flow annular water inlet device
7 be ultraviolet producer connection jaws 18 is taper type water distributor
8 be cathode connection mouth 19 is negative plate draw-in groove
9 be anode connection mouth 20 is positive plate draw-in groove
10 is net formula tubular titanium negative plate
Embodiment
Below in conjunction with accompanying drawing and embody rule embodiment, the invention will be further described, and specific embodiment does not form technical scheme of the present invention and limits.
As shown in Figure 1-2, ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor wall internal layer of the present invention is formed by the hard PVC seamless welding of acid and alkali-resistance, and skin is aided with closed stainless steel plate, makes equipment possess certain insulativity and resistance to pressure.Ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor inside is followed successively by ring-type spoke stream negative pressure suction type internal recycle water inlet system 2 and photoelectrocatalysioxidization oxidization reactive system according to order from bottom to top, wherein ring-type spoke stream negative pressure suction type internal recycle water inlet system 2 is connected with reactor water-in 12 and reactor sludge hopper 1, ring-type spoke stream negative pressure suction type internal recycle water inlet system 2 is constructed as follows: spouting of liquid pipe 16 is connected with length adjustable connecting tube 14 at its spouting of liquid pipe venturi 15 place, length adjustable connecting tube 14 is connected with radial-flow annular water inlet device 17 again, radial-flow annular water inlet device 17 gathers isometrical circular hole, radial-flow annular water inlet device 17 diameter is preferably 2/3 reactor inside diameter, its effect is pumped to by reactor bottom contact zone effluent liquid in ring-type spoke stream negative pressure suction type internal recycle water inlet system, and enter in photoelectrocatalysioxidization oxidization reactive system by spouting of liquid pipe 16, spouting of liquid pipe 16 top water outlet is connected with taper type water distributor 18, wherein gather isometrical circular hole at taper type water distributor 18 top, Circularhole diameter R < 0.3cm, upper strata photoelectric 3 is avoided to run off, taper type water distributor 18 effect is homogenized at the water outlet of ring-type spoke stream negative pressure suction type internal recycle water inlet system 2, taper type water distributor 18 is connected with back up pad 13, wherein back up pad 13 there are negative plate draw-in groove 19 and positive plate draw-in groove 20, negative plate draw-in groove 19 diameter equals net formula tubular Ti cathode 10 diameter, positive plate draw-in groove 20 diameter equals board-like tubular DSA anode 11 diameter, act as fixing cathode-anode plate, back up pad 13 is gathered isometrical circular hole, back up pad 13 diameter equals reactor inside diameter, effect is support photoelectrocatalysioxidization oxidization system, and stationary ring spoke stream negative pressure suction type internal recycle water inlet system 2, photoelectrocatalysioxidization oxidization system is board-like tubular DSA anode 11, photoelectric 3, net formula tubular Ti cathode 10, ultraviolet producer 4 from outside to inside successively, between board-like tubular DSA anode 11 and net formula tubular Ti cathode 10, spacing is 0.5-2cm, central filler photoelectric 3, run off for preventing photoelectric 3, wherein bottom and top layer catalyzer median size are 0.3-0.5cm, middle layer catalyzer median size is 0.1-0.3cm, and the dosage of catalyzer is 1:200-1:20 with the mass ratio of waste water in reaction.Comprise ultraviolet producer 4 in net formula tubular Ti cathode inside, be preferably the one in 200-400nm high voltage mercury lamp, medium pressure mercury lamp and ultraviolet lamp, power is 4-200W.After process, water outlet is discharged through reactor water port 5, reactor head vapor pipe is connected with gas injection tube 6 venturi, the air outlet of gas injection tube and air lead directly to, be 0.2-1mpa pressurized air by blasting pressure in gas injection tube 6, form negative pressure at gas injection tube 6 venturi place, the hydrogen that suction inside reactor produces also is diluted to concentration and enters in air after 4%.
Specific examples one:
Zhejiang petro-chemical corporation is due to refined oil product complexity, and cause containing a large amount of recalcitrant substance in factory effluent, this waste water COD after biochemical treatment is 300-500mg/L, cannot reach relevant Chinese effluent standard.Ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor of the present invention is adopted to carry out engineering Application Research to the advanced treatment of the said firm's bio-chemical effluent, it is 1h that hydraulic detention time is worked as in result display, when ton water power consumption is for 15kw.h/t, water outlet COD≤60mg/L, water outlet meets qualified discharge water quality requirement, compared with traditional aeration type internal recycle optoelectronic device, under the condition that treatment effect is constant, ton water power consumption about reduces 1-2kw.h electric energy.
Specific examples two:
Tianjin petro-chemical corporation oil refining wastewater is after biochemical treatment, for realizing waste water near zero release, adopt the two membranous system reuse part bio-chemical effluent of filtration-reverse osmosis, a certain amount of concentrated solution can be produced after two membranous system process, this concentrated solution COD is about 300-400mg/L, specific conductivity is about 9000-12000 μ s/cm, Cl
-content is about 2000-3000mg/L, and this concentrated solution is because its saltiness is high, discharge capacity is little, contents is blamed with features such as biochemical degradations, should not again adopt biochemical process process.After adopting ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor of the present invention process, when hydraulic detention time in reactor is 1h, when ton water power consumption is for 14kw.h/t, water outlet COD≤50mg/L, meet qualified discharge water quality requirement, compared with traditional aeration type internal recycle optoelectronic device, save 2-3kw.h electric energy.
Claims (9)
1. a ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor, it is characterized in that: described reactor head is provided with gas injection tube, the inlet mouth of described gas injection tube is connected with air driven pump, and the venturi of gas injection tube is connected with reactor head vapor pipe; The air outlet of described gas injection tube and air lead directly to, and by blasting pressurized air with pressure in gas injection tube, near gas injection tube venturi, form negative pressure, and the hydrogen that suction inside reactor produces also dilutes, and is then discharged in air by vapor pipe;
Described inside reactor mainly comprises photoelectrocatalysioxidization oxidization reactive system and the ring-type spoke stream negative pressure suction type internal recycle water inlet system be connected; The bottom of described reactor is provided with the reactor water inlet pipe arranged bottom sludge hopper and sludge hopper; Described reactor water inlet pipe is connected with the spouting of liquid pipe of described ring-type spoke stream negative pressure suction type internal recycle water inlet system, throw out periodic exhaustion in sludge hopper;
Described ring-type spoke stream negative pressure suction type internal recycle water inlet system comprises the spouting of liquid pipe in the middle of water inlet system, bottom described spouting of liquid pipe, water-in is connected with reactor water inlet pipe, in the middle of spouting of liquid pipe, venturi place has some length adjustable pipelines to be connected with the ring-type radial-flow water inlet device of the densely covered isometrical circular hole being positioned at reactor bottom region, spouting of liquid pipe top is connected with a taper type water distributor, gather isometrical water distributing pore at described taper type water distributor top, and be connected with the back up pad being densely covered with isometrical circular hole, described back up pad is used for support photoelectrocatalysioxidization oxidization reactive system and stationary ring spoke stream negative pressure suction type internal recycle water inlet system,
Described photoelectrocatalysioxidization oxidization reactive system comprises setting one piece of board-like tubular DSA anode on the supporting plate and one piece of net formula tubular Ti cathode, and be filled with granular photoelectric between cathode-anode plate, net formula tubular Ti cathode inside is provided with ultraviolet producer;
Wherein said water distributing pore diameter is less than described granular photoelectrocatalysis oxidant layer bottom minimum grain size.
2. ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor according to claim 1, described back up pad is provided with a hollow cathode board groove and a circular anode board groove, annular slot diameter equals corresponding tubular pole plate diameter, and back up pad diameter equals reactor inside diameter; Diameter that described ring-type radial-flow water inlet device gathers is less than the circular hole of 0.3cm, and ring-type radial-flow water inlet device diameter is 0.5-0.8 times of reactor inside diameter.
3. ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor according to claim 1, it is characterized in that, described reactor is cylindrical, and wall internal layer material is hard PVC, PPR corrosion resistant material, and outer material is stainless steel.
4. ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor according to claim 1, it is characterized in that, described board-like tubular DSA positive plate is the precious metal anode plate that titanium substrate surface supported noble metals material is prepared from, and precious metals species adopts one or more materials in platinum, ruthenium, iridium, rubidium and Zirconium oxide to form; Described board-like tubular DSA anode and described net formula tubular Ti cathode polar plate spacing are 0.5-2cm.
5. ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor according to claim 1, it is characterized in that, the granular photoelectric of described inside reactor adopt in Alpha-alumina or silicon-dioxide one or more be carrier, one or more active substances formation in surface load titanium dioxide, Cadmium Sulfide, ferric oxide, Manganse Dioxide; And be prepared into honeycomb vesicular structure.
6. ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor according to claim 1, it is characterized in that, described photoelectric layering is filled between cathode-anode plate, wherein bottom and top layer photoelectric median size maximum, particle diameter is at 0.3cm ~ 0.5cm; Middle layer catalyzer median size is minimum, and particle diameter is at 0.1cm ~ 0.3cm, and the dosage of described granular photoelectric is 1:200-1:20 with the mass ratio of waste water in reaction; Described water distributing pore diameter R is less than 0.3cm.
7. ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor according to claim 1, it is characterized in that, one in the high voltage mercury lamp of described inside reactor photoelectrocatalysioxidization oxidization system medium ultraviolet producer to be wavelength be 200-400nm, medium pressure mercury lamp and ultraviolet lamp, power is 4-200W.
8. ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor according to claim 7, it is characterized in that, described ultraviolet producer profile is cylindrical, and its external diameter equals netted cartridge type titanium negative plate internal diameter.
9. ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor according to claim 1, it is characterized in that, the air outlet of gas injection tube is directly connected with air, by blasting the pressurized air that pressure is 0.2-1Mpa, negative pressure state is formed at gas injection tube venturi place, the hydrogen sucking-off that inside reactor is produced also is diluted to concentration less than 4%, finally enters air.
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| CN104944511B (en) * | 2015-05-27 | 2017-12-08 | 北京大学 | The method and apparatus that a kind of photoelectrocatalysis removes heavy metal ions in wastewater |
| CN105236685A (en) * | 2015-10-28 | 2016-01-13 | 中国海洋石油总公司 | Zero-discharge treatment method for offshore-platform domestic sewage |
| CN105967313B (en) * | 2016-06-21 | 2019-03-05 | 中国海洋石油集团有限公司 | Photoelectrocatalysioxidization oxidization combined treatment device is recycled in a kind of |
| CN110564586A (en) * | 2019-09-18 | 2019-12-13 | 南昌绿锦茶疗食品有限公司 | Pipeline negative pressure type photobioreactor |
| CN111606518A (en) * | 2020-06-09 | 2020-09-01 | 闫娟 | Comprehensive treatment method for coal coking wastewater |
| CN112777818B (en) * | 2020-12-13 | 2022-11-15 | 中海油天津化工研究设计院有限公司 | Composite membrane photoelectrocatalysis fluidized bed treatment device and method |
| CN113354194A (en) * | 2021-06-04 | 2021-09-07 | 清华大学 | Device for cooperatively treating printing waste gas and waste water and method for treating printing waste gas and waste water |
| CN115159630A (en) * | 2022-06-20 | 2022-10-11 | 天津正达科技有限责任公司 | Integrated internal circulation electro-catalytic reactor |
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