CN108996698A - A kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa - Google Patents
A kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa Download PDFInfo
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- CN108996698A CN108996698A CN201810751816.6A CN201810751816A CN108996698A CN 108996698 A CN108996698 A CN 108996698A CN 201810751816 A CN201810751816 A CN 201810751816A CN 108996698 A CN108996698 A CN 108996698A
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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Abstract
The present invention relates to a kind of hydrogen matrix biopolymers palladium reactors being aerated with non-porous hollow tunica fibrosa, comprising: main reactor: including main reactor tube body, the first non-porous hollow fiber film component for being provided at its inner portion along main reactor tube body and being attached with biological palladium and the first hydrogen inlet that the first non-porous hollow fiber film component upper and lower ends are arranged in；Auxiliary reactor: including auxiliary reactor tube body, the second non-porous hollow fiber film component for being provided at its inner portion along auxiliary reactor tube body and being attached with biological palladium and the second hydrogen inlet that the second non-porous hollow fiber film component upper end is arranged in；Main reactor and auxiliary reactor composition are connected by circulation and connect external hydrogen gas source and water system.Compared with prior art, structure of the invention is reasonable, can be used for recycling and fixing palladium element in water, can control hydrogen air demand, and high treating effect improves hydrogen utilization ratio, avoids gas diffusion caused by on-way resistance is uneven and utilization rate is low etc..
Description
Technical field
The present invention relates to a kind of bioreactors, raw more particularly, to a kind of hydrogen-based matter with non-porous hollow tunica fibrosa aeration
Object palladium reactor.
Background technique
Oxidation contact scar is extremely serious in the underground water in many areas in China, these oxidative pollutants mainly have nitric acid
Salt, sulfate, bromate, perchlorate, chromate plasma compound, organic chloride such as chloroform, chlorophenol, trichloro ethylene
Deng.
For chemical catalysis reduction-oxidation contact scar object, Metal Palladium (Pd) is a kind of common effective catalyst, but due to
Palladium it is expensive, therefore, how to reduce the technical costs based on palladium catalyst become current research one of emphasis.For this purpose,
There is method of the research by micro-reduction in recent years, reduction prepares Technique of Nano Pd (biological palladium) from the waste water containing palladium ion, into
And its excellent catalytic reduction performance is utilized, it realizes to water oxygen contact scar object high-efficiency detoxicating.But has and biological palladium is ground
Study carefully and mostly occur in shaking flask, biological palladium is easily lost with water flow, is not easy to for biological palladium to be used for the processing of actual waste water, therefore is badly in need of
Exploitation one reactor assembly convenient for offer hydrogen, preparation and fixed biological palladium.
Hydrogen-based matter technology of biological membrane is that have cleaning, hydrogen utilization ratio using autotrophic microbe reduction-oxidation contact scar object
The advantages that high, low in cost, without secondary pollution, the underground water and drinking water lacked suitable for organic carbon source.The technology uses hydrogen
Gas is as electron donor, hollow-fibre membrane biofilm carrier and gas delivery passage.Hydrogen is diffused into film out of hollow-fibre membrane
Outside, envelope surface microorganism utilizes；Oxidative pollutant is reduced under microbial action, and water body is purified, such as nitric acid
Salt is reduced to nontoxic nitrogen, and perchlorate is reduced to nontoxic chloride ion.
Chinese patent CN200810202126.1 discloses a kind of device for handling oxidative pollutant in drinking water, reaction
Magnetic stirring apparatus is arranged in device cylinder body bottom, and bottom is the fixation bracket base consolidated with cylinder inboard wall, and inner barrel, which has, passes through fibre
The detachable hollow fiber film assembly that hollow-fibre membrane and membrane module end sleeve are consolidated and sealed by dimension film band, film group
The end sleeve of part is consolidated by internal screw thread fastening sleeve respectively at the membrane module bracket of cylinder body bottom and top and blind flange
Membrane module fixing piece connects, and hydrogen pipe fitting is arranged on blind flange.Hydrogen enters in hollow-fibre membrane through membrane module end sleeve
Portion is diffused into film wire outer surface in a manner of still diffusion.It is practiced by longtime running, the hydrogen-based matter biomembrane in above-mentioned patent
Reactor for treatment works well, stable, but there are problems that following 8: 1) the PVDF Hollow Fiber Ultrafiltration in above-mentioned patent
Film film wire is relatively large in diameter (1.0-3.0mm), and film is long and film wire radical is limited by reactor size, and film wire radical is limited, reaction
Small 2) the reactor volume of film surface product of device unit volume is big, and mixed flow effect is poor, is unfavorable for biofilm detachment and regeneration.3) there is hole
Film is easily carbonated the blocking of the precipitatings such as calcium, while can not restore Pd2+Technique of Nano Pd is prepared, film surface, which accumulates the precipitatings such as calcium carbonate, influences hydrogen
Gas transmission.4) when acquiring film wire sample, membrane module is exposed in air, and meeting disrupting biofilm influences reactor operational effect.5)
Reactor lacks air-tightness, and air easily enters inside.6) porose PVDF hollow-fibre membrane is not withstand pressure, is easy gas leakage, and hydrogen seeps
Saturating coefficient is larger, and hydrogen is easy to overflow, and the hydrogen infiltration number of same membrane material is inconsistent, it is difficult to determine hydrogen by supplying air pressure
Air flux.7) the certain oxidative pollutant effects difficult to degrade of micro-reduction are also unstable, vulnerable to such environmental effects, to spy
The domestication time for determining pollutant process is long, not anti impulsion load；8) inside reactor has large volume of head space, H2From solution
Spilling is accumulated in inside reactor head space, and making may be containing the biggish hydrogen of concentration in head space, and there are security risks.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind with non-porous hollow fibre
Tie up the hydrogen matrix biopolymers palladium reactor of film aeration.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa, the reactor include:
Main reactor: it including main reactor tube body, is provided at its inner portion along main reactor tube body and is attached with biological palladium
First non-porous hollow fiber film component and the first hydrogen gas that the first non-porous hollow fiber film component upper and lower ends are set
Mouthful, main reactor tube body upper end side is equipped with main reactor reflux water out, and main reactor bottom of the pipe side is set
There is main reactor reflux water inlet；
Auxiliary reactor: it including auxiliary reactor tube body, is provided at its inner portion along auxiliary reactor tube body and is attached with biological palladium
Second non-porous hollow fiber film component and the second hydrogen inlet that the second non-porous hollow fiber film component upper end is set,
Auxiliary reactor tube body upper end side is equipped with auxiliary reactor reflux water inlet, and the other side is equipped with reactor water outlet, the pair
Reactor bottom of the pipe side is equipped with auxiliary reactor reflux water out, and the other side is equipped with reactor water inlet；
The main reactor reflux water out is connected with auxiliary reactor reflux water inlet, the auxiliary reactor reflux
Water out and main reactor reflux water inlet are connected, first hydrogen inlet and the second hydrogen inlet and hydrogen source phase
Connection, the reactor water inlet are connected with water system.
Preferably, the first non-porous hollow fiber film component and the second non-porous hollow fiber film component are respectively by complex root
First non-porous hollow fiber film wire and the second non-porous hollow fiber film wire are made, and the quantity of the first non-porous hollow fiber film wire is more
In the second non-porous hollow fiber film wire.
It is furthermore preferred that the first non-porous hollow fiber film wire is equipped with 50, the second non-porous hollow fiber film wire is set
There are 10.
It is furthermore preferred that the first non-porous hollow fiber film wire is identical with the second non-porous hollow fiber film wire, adopt
It is made with polypropylene, effective length 27cm, outer diameter is 200 μm, and internal diameter is 100 μm.
Preferably, the first non-porous hollow fiber film component both ends are arranged with hermetically passing main reactor tube body two respectively
The first sleeve of the first hydrogen inlet is held and has, the second non-porous hollow fiber film component upper end is arranged with hermetically passing
Auxiliary reactor tube body and the second sleeve for having the second hydrogen inlet.
Preferably, which is characterized in that the first non-porous hollow fiber film component both ends pass through aperture plastic spiral cover respectively
It is fixed with the main reactor tube body；
The second non-porous hollow fiber film component upper end passes through aperture plastic spiral cover and auxiliary reactor tube body upper end
Fixed, the second non-porous hollow fiber film component lower end is fixedly connected under the auxiliary reactor tube body by nonporous plastic spiral cover
End.
It is furthermore preferred that between the aperture plastic spiral cover and main reactor tube body, the aperture plastic spiral cover and side reaction
Sealing rubber washer is equipped between device tube body, between the nonporous plastic spiral cover and auxiliary reactor tube body.
Preferably, the main reactor reflux water out and auxiliary reactor reflux water inlet, auxiliary reactor reflux water out
Pass through hose with main reactor reflux water inlet to connect, and in auxiliary reactor reflux water out and main reactor reflux water inlet
Between be additionally provided with circulating pump.
Preferably, first hydrogen inlet and the second hydrogen inlet connect external hydrogen by hose connection one
The four-way pipe in source.
Preferably, the main reactor tube body and auxiliary reactor tube body are cylinder, and material is quartz glass.
A kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa, biological palladium are fixed on the first non-porous hollow
In fiber film wire and the second non-porous hollow fiber film wire.The biology palladium can be by containing Pd2+Solution preparation, specific preparation method
Are as follows: it is inoculated with sewage plant anaerobic sludge in the reactor and uses the culture of inorganic medium continuum micromeehanics, to hollow-fibre membrane
Upper change water inlet component after forming thick and solid biomembrane, by the Pd of 200mg/L2+Culture medium is introduced, continuum micromeehanics run 7d, water inlet
Flow velocity is 0.09ml/min, hydraulic detention time 11.5h, hydrogen partial pressure 1atm；After reaction, hollow fiber membrane surface
Cover the biological palladium of one layer of black.Culture medium prescription: by 0.1g NaHCO3、0.2g KH2PO4、0.15mg CaCl2·2H2O,
2mg MgCl2·6H2O, 1ml acidity trace element solution, 1ml alkalinity trace element solution are added into 1 liter of deionized water, match
At culture medium, pH 6.5；Acid trace element solution refers to: 10ml 25%HCl, 1.5g being added in every liter of deionized water
FeCl2·4H2O、0.19g CoCl2·6H2O、0.1g MnCl2·4H2O、70mg ZnCl2、6mg H3BO3、36mg
Na2MoO4·2H2O、24mg NiCl2·6H2O、2mg CuCl2·2H2O；Alkaline trace element solution refers to: every liter of deionization
0.5g NaOH, 6mg Na are added in water2SeO3·5H2O、8mg Na2WO4·2H2O.It is specific about reactor start-up and operation etc.
Operation is well known to those skilled in the art, therefore is not explained in detail.
The water system includes water inlet tank and intake pump, and intake pump selects peristaltic pump, by water from water inlet tank extraction, with perseverance
Constant current speed is from reactor water inlet continuum micromeehanics.
Apparatus of the present invention are with a wide range of applications in the water body processing that oxidative substance pollutes, and are such as applied to contain
It is the groundwater in mining area of chromate, the waste water containing nitrate, dry-cleaning industry and underground water containing organic chloride, dirty containing high oxidation state
Contaminate the industrial wastewater etc. of object.
Mentality of designing of the present invention is each a branch of non-porous polypropylene hollow fiber of device in the major and minor two branch pipes body of reactor
Film carries out bubble-free aeration, is carried out purified treatment by the water body of oxidation state contaminants to poor carbon source using biological palladium.
The shape of reactor tube body of the invention is slender cylinder, and tube body uses small internal diameter, certain in dischargeable capacity
In the case of can accommodate more film wires.Reactor tube body can continuum micromeehanics, two each devices of tubular body a branch of non-porous poly- third
Alkene hollow-fibre membrane, membrane module are fixed on reactor tube body by aperture plastic screw cap, can be cleaned and be replaced offline；The
H continuously is passed through to inside reactor using the method that no vacuolar membrane is aerated in one non-porous hollow fiber film component2, H2Ventilatory capacity is controllable,
It can avoid excess H2It overflows, operational safety and efficiently utilization；If using having hole doughnut film preparation Technique of Nano Pd, Pd in solution2+
It can be entered inside hollow-fibre membrane by fenestra, Technique of Nano Pd simple substance is generated inside film wire and blocks fenestra, causes hydrogen can not be from
Film surface is diffused in film, influences the H of tunica fibrosa2Ventilatory capacity, and the non-porous film preparation Technique of Nano Pd of the polypropylene is not in
The phenomenon, while can reduce and block the influence that fenestra hinders hydrogen transmission because of film surface precipitating；Hollow fiber membrane surface it is micro-
Biology couples to form biological palladium with Technique of Nano Pd depth, has good fixed function to Technique of Nano Pd, prevents the loss of palladium；Reactor
Water outlet uses gas sampling bag to collect, and reactor assembly has good air-tightness, avoids during whole service and sky
Gas contact, reduces O2Influence to treatment effect, the hydrogen in simultaneous reactions device, which is also difficult to overflow, to be dissipated, and improves H2Utilization rate and safety
Property；Since reactor volume is smaller, mix solution in reactor more evenly by high speed reflux.In addition, in main reactor
The ventilation of membrane module upper and lower ends avoids the problem that gas diffusion caused by on-way resistance is uneven and utilization rate is low.
In group holding reactor, by the aperture plastic spiral cover with rubber washer by the first non-porous hollow fiber film component,
Second non-porous hollow fiber film component and main reactor tube body, auxiliary reactor tube body closely link into an integrated entity, main reactor tube body
It is closely connected between auxiliary reactor tube body with hose, guarantees the stringent air-tightness of reactor；Reactor water outlet uses gas sampling
Bag is collected, and air is avoided to enter in reactor.
When reactor assembly of the present invention is run, H2Enter the first non-porous hollow tunica fibrosa by gas piping with certain pressure intensity
The inside of silk and the second non-porous hollow fiber film wire, permeates in membrane material, is entered in a manner of still diffusion from film surface outer
Portion's water body.It is hydraulically full in reactor, no headspace gas.Auxiliary reactor flows back between water inlet and main reactor reflux water out
It is connected with hose, intermediate to make to form reflux in tube body through circulating pump, making water flow in reactor is in be thoroughly mixed stream.In hydrogen warp
It after empty fiber membrane diffusion, then spreads from biological palladium interior, while water pollutant is outside biological palladium by internally spreading,
The reaction rate of hydrogen and substrate can be improved in this reverse diffusion.Biological palladium utilizes hydrogen using oxidative pollutant as electron acceptor
The electronics of offer will aoxidize contact scar and be reduced into non-toxic or low-toxic form, and reduzate or formation precipitating are adsorbed by biological palladium,
Or it returns in water.Purified water outlet is flowed out by the water outlet at the top of auxiliary reactor using gravity.
The present invention considers in process of experimental, needs the film wire sampling analysis to reactor, ingress of air when taking film
The biological palladium on membrane module and surface can be all damaged with mechanical disturbance, therefore reactor is divided into two reactors of major-minor, main reaction
The hollow fiber film thread of the first membrane module in device is more (50), the second mould for the processing of pollutant, in auxiliary reactor
The hollow fiber film thread of component is less (10), be mainly used for film wire sampling, avoid influence main reactor in first it is non-porous in
Empty fiber membrane component, to avoid influencing reactor operational effect.
Compared with prior art, the invention has the following beneficial effects:
(1) the non-porous hollow tunica fibrosa used in the present invention provides technical conditions to prepare Technique of Nano Pd, while reducing hollow
Fiber film surface precipitates the adverse effect spread to hydrogen.If using having hole doughnut film preparation Technique of Nano Pd, Pd in solution2+Meeting
Entered inside hollow-fibre membrane by fenestra, Technique of Nano Pd simple substance is generated inside film wire and blocks fenestra, causes hydrogen can not be from film
Film surface is inside diffused to, the H of tunica fibrosa is influenced2Ventilatory capacity, and the non-porous film preparation Technique of Nano Pd of the polypropylene is not in this
Phenomenon, while can reduce and block the influence that fenestra hinders hydrogen transmission because of film surface precipitating.
(2) the film wire outer diameter that the present invention uses is smaller, and large specific surface area can be accommodated in the case where dischargeable capacity is certain
More film wires increase the film surface product of reactor unit volume.
(3) biomembrane is coupled the biological palladium to be formed with Technique of Nano Pd depth and is fixed on hollow fiber membrane surface by the present invention,
Catalysis reduction effect is significantly larger than the treatment effect of simple biomembrane, and does not change influence, anti-pollution object vulnerable to environmental factor
Impact load, reactor start-up is short, does not need the microbial acclimation time.
(4) the non-porous film bubble-free aeration technology that the present invention uses further promotes gas phase in water phase compared to micropore bubble-free aeration
In dissolution, reacted due to infiltration coefficient of the hydrogen in the film wire it is known that hydrogen can also be controlled by adjusting hydrogen partial pressure
Flux in device improves gas effciency, had not only guaranteed hydrogen supply but also excess hydrogen in water is avoided to overflow.
(5) the reactor tube body in the present invention is elongate cylinder, and volume is smaller, and the liquid at high speed be conducive in reactor is returned
Stream makes have the removal using pollutant in state is thoroughly mixed in reactor.
(6) hydraulically full in reactor of the invention, no headspace gas accumulation avoids the danger of head space hydrogen explosion.
(7) ventilation of first non-porous hollow fiber film component upper and lower ends avoids on-way resistance in main reactor of the invention
The problem that bring gas diffusion is uneven and utilization rate is low.
(8) reactor of the invention water outlet is collected using gas sampling bag, and reactor assembly has good air-tightness,
It avoids during whole service and is contacted with air, reduce O2Influence to treatment effect, the hydrogen in simultaneous reactions device are also difficult
It is dissipated with overflowing, improves H2Utilization rate and safety.
(9) membrane module is fixed on reactor tube body by aperture plastic screw cap in reactor of the invention, Ke Yili
Line cleaning and replacement.
(10) the configuration of the present invention is simple is reasonable, and treatment effect is excellent, stable, easy to maintain, and Pd in water can be recycled2+And
Oxidative pollutant in permanently effective processing drinking water, underground water and particular industry waste water.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of reactor body of the present invention；
Fig. 2 is the process flow diagram of reactor of the present invention；
Shown in figure label:
1- the first non-porous hollow fiber film component, 2- the first non-porous hollow fiber film wire, the first hydrogen inlet of 3-, 4- master
Reactor tube body, 5- aperture plastic spiral cover, 6- rubber washer, 7- main reactor reflux water inlet, 8- main reactor recirculation water go out
Mouthful, 9- auxiliary reactor flows back water out, and 10- auxiliary reactor flows back water inlet, 11- the second non-porous hollow fiber film component, 12- the
Two non-porous hollow fiber film wires, the second hydrogen inlet of 13-, 14- auxiliary reactor tube body, 15- reactor water inlet, 16- reaction
Device water outlet, 17- nonporous plastic spiral cover, 18- first sleeve, 19- second sleeve, 20- circulating pump, 21- intake pump, 22- water inlet
Tank.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
In following embodiment unless otherwise instructed, then it represents that used raw material etc. are existing structure or existing commercially available
Product is prepared using existing already known processes.
Embodiment 1
A kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa, as shown in Figure 1, the reactor includes:
Main reactor: including main reactor tube body 4, it is arranged in inside main reactor tube body 4 and is attached with biological palladium first
Non-porous hollow fiber film component 1, and first hydrogen inlet 3 at 1 both ends of the first non-porous hollow fiber film component is set, it is main
4 upper end side of reactor tube body is equipped with main reactor reflux water out 8, and 4 lower end side of main reactor tube body is equipped with main reactor
Flow back water inlet 7, and the first non-porous hollow fiber film component 1 includes the first non-porous hollow being vertically arranged along main reactor tube body 4
Fiber film wire 2；
Auxiliary reactor: including auxiliary reactor tube body 14, the biological palladium that is attached with inside auxiliary reactor tube body 14 is set
Second non-porous hollow fiber film component 11, and the second hydrogen gas of 11 upper end of the second non-porous hollow fiber film component is set
Mouth 13,14 upper end side of auxiliary reactor tube body are equipped with auxiliary reactor reflux water inlet 10, and the other side is equipped with reactor water outlet 16,
14 lower end side of auxiliary reactor tube body is equipped with auxiliary reactor reflux water out 9, and the other side is equipped with reactor water inlet 15, the second nothing
Hole hollow fiber film assembly 11 includes the second non-porous hollow fiber film wire 12 being vertically arranged along auxiliary reactor tube body 14；
Main reactor reflux water out 8 and auxiliary reactor reflux water inlet 10 is connected, auxiliary reactor flow back water out 9 and
Main reactor reflux water inlet 7 is connected, and the first hydrogen inlet 3 and the second hydrogen inlet 13 are connected with hydrogen source, instead
Device water inlet 15 is answered to be connected with water system.
First non-porous hollow fiber film wire 2 is equipped with 50, and the second non-porous hollow fiber film wire 12 is equipped with 10, first
Non-porous hollow fiber film wire 2 is identical with the second non-porous hollow fiber film wire 12, is all made of the nothing of Japanese Di Ren company production
Hole polypropylene hollow fiber membrane silk, effective length 27cm, outer diameter are 200 μm, and internal diameter is 100 μm.First non-porous hollow fiber
1 upper and lower ends of membrane module are arranged with first sleeve 18 respectively, and 11 upper end of the second non-porous hollow fiber film component is arranged with second set
Cylinder 19.First non-porous hollow fiber film component 1 is fixed on 4 both ends of main reactor tube body by aperture plastic spiral cover 5；Second is non-porous
11 upper end of hollow fiber film assembly is fixed on 14 upper end of auxiliary reactor tube body by aperture plastic spiral cover 5, and the second non-porous hollow is fine
Dimension 11 lower end of membrane module is fixed on 14 lower end of auxiliary reactor tube body, aperture plastic spiral cover 5 and main reaction by nonporous plastic spiral cover 5
Between device tube body 4, between aperture plastic spiral cover 5 and auxiliary reactor tube body 14, nonporous plastic spiral cover 17 and auxiliary reactor tube body 14
Between, it is equipped with rubber washer 6, guarantees device air-tightness.Main reactor reflux water out 8 is flowed back by hose and auxiliary reactor
Water inlet 10 is connected；Auxiliary reactor reflux water out 9 connects main reactor reflux water inlet 7 through circulating pump 20 by hose.
First hydrogen inlet 3 connects four-way pipe by hose with the second hydrogen inlet 13, and is connected with extraneous hydrogen source.It is main anti-
It answers device tube body 4 and auxiliary reactor tube body 14 is cylinder, material is quartz glass, tube body long 33cm, outer diameter 13mm, internal diameter
11mm, effective volume 30mL.
In reactor, biological palladium is fixed in the first non-porous hollow fiber film wire 2 and the second non-porous hollow fiber film wire 12.
The present embodiment is used to handle the oxidative pollutant in drinking water, underground water and industrial wastewater.
In group holding reactor, main reactor tube body 4 and auxiliary reactor tube body 14 need to be made first, be that quartz glass is burnt
Then the double glazing pipe of the TBE (threaded both ends) of system makes matched with main reactor tube body 4 and 14 both ends of auxiliary reactor tube body
Aperture plastic spiral cover 5 and rubber washer 6, main reactor reflux water out 8 and auxiliary reactor reflux water inlet 10 pass through hose and connect
Connect, main reactor water inlet 7 and auxiliary reactor the reflux water out 9 that flows back is connected by hose, by reactor be connected as one it is whole
Body.
Then the first non-porous hollow fiber film component 1 and the second non-porous hollow fiber film component 11 are successively assembled.First nothing
Hollow fiber film thread 2 both ends in hole are cemented in first sleeve 18 using epoxide-resin glue, guarantee the first non-porous hollow fiber film wire 2
It is firmly bonded and seamless, and the opening blow-by at every first non-porous hollow fiber film wire, 2 both ends, protects with first sleeve 18
Card hydrogen can be transferred through both ends open and enter inside the first non-porous hollow fiber film wire 2, then be diffused into outside film；Second non-porous hollow
12 one end of fiber film wire is cemented in second sleeve 19 using epoxide-resin glue, guarantees the second non-porous hollow fiber film wire 12 and the
Two sleeves 19 are firmly bonded and seamless, and are open blow-by with the hollow fiber film thread of 19 cementation one end of second sleeve, are protected
Card hydrogen can be transferred through opening and enter inside the second non-porous hollow fiber film wire 12, then be diffused into outside film, and other end epoxy
Resin glue sealing；First non-porous hollow fiber film component 1 is packed into main reactor tube body 4, the first non-porous hollow fiber film component 1
The first sleeve 18 at both ends is sequentially inserted into rubber washer 6 and aperture plastic spiral cover 5 and is cemented in aperture with epoxide-resin glue
On plastic spiral cover 5, the second non-porous hollow fiber film component 11 is packed into auxiliary reactor tube body 14, the second non-porous hollow tunica fibrosa group
The second sleeve 19 of 11 upper end of part is sequentially inserted into rubber washer 6 and aperture plastic spiral cover 5 and is cemented in epoxide-resin glue
On aperture plastic spiral cover 5.
After reactor is completed, according to process flow chart shown in Fig. 2, by the tank 22, intake pump 21, circulating pump of intaking
20, reactor body (the present embodiment assembling), water inlet pipe, return pipe, outlet pipe, effluent collection bag connect completely with hydrogen pipe.
When the present embodiment device is run, H2With certain pressure intensity by gas piping, into the first non-porous hollow fiber film wire 2
It is diffused to outside film wire in a manner of still diffusion inside the second non-porous hollow fiber film wire 12, then through film wire surface.Into
Water pump 21 selects peristaltic pump, with constant flow rate from 15 continuum micromeehanics of reactor water inlet, relies on gravity from reactor water outlet 16
From outflow water, no headspace.It is connected between auxiliary reactor reflux water out 9, main reactor reflux water inlet 7 with hose, in
Between through peristaltic pump provide power so that form reflux in main reactor tube body 4 and auxiliary reactor tube body 14, the liquid in reactor
Flowing is in be thoroughly mixed stream.Hydrogen is spread after hollow fiber membrane surface is spread, then by the interior of biological palladium, while water
In pollutant by internally being spread outside biological palladium, reverse diffusion improves hydrogen and pollutes the reaction rate of substrate.Biology
Palladium will be aoxidized using water oxygen contact scar object as substrate using the electronics provided from the hydrogen molecule of hollow-fibre membrane diffusion into the surface
Contact scar object is reduced into low toxicity or nontoxic form, and reduzate or formation precipitating are attached to film wire surface, or in water outlet.
Underground water containing nitrate is handled using reactor assembly in the present embodiment, NO of intaking3 -- N concentration is 5-20mg/
L, flow velocity 0.18ml/min of intaking, hydraulic detention time 5.7h, it is 1atm that hydrogen, which supplies pressure, and film surface maximum reduction flux is
505mg NO3 --N/(m2·d).Reactor start-up: with sterilizing syringe by the municipal sewage plant 10ml anaerobic pond activated sludge
(MLSS=3000mg/L) it squeezes into and carries out biofilm in the reactor full of culture medium, hollow fiber membrane surface preliminarily forms after 2 days
Start continuum micromeehanics after biomembrane, the nitrate salt then carried out 90 days tames startup stage.Then it introduces and contains into reactor
There is the water inlet of sodium tetrachloropallate, continuum micromeehanics 8 days, prepares biological palladium in the reactor.After biological palladium is formed, change nitre in water inlet
Hydrochlorate concentration, after each influent concentration is run 3 days, nitrate concentration is zero in water outlet, is discharged pH between 7-7.5.
Simulated wastewater containing chromate is handled using the reactor assembly of the present embodiment, water inlet Cr (VI) concentration is 1-
10mg/L, flow velocity 0.18ml/min of intaking, hydraulic detention time 5.7h, it is 1atm, the reduction of film surface maximum that hydrogen, which supplies pressure,
Flux is 241mgCr (VI)/(m2·d).Reactor start-up: with sterilizing syringe that the municipal sewage plant 10ml anaerobic pond is living
Property sludge (MLSS=3000mg/L), which is squeezed into the reactor full of culture medium, carries out biofilm, after 2 days at the beginning of hollow fiber membrane surface
Step starts continuum micromeehanics after forming biomembrane, and the nitrate salt then carried out 90 days tames startup stage.Then into reactor
The water inlet containing sodium tetrachloropallate is introduced, continuum micromeehanics 8 days, prepares biological palladium in the reactor.After biological palladium is formed, change into
Concentration of chromate in water, after the water inlet of each concentration is run 3 days, chromate removal rate reaches 99% or more in water outlet, is discharged pH
Between 7-7.5.
Comparative example 1
Use structure same as Example 1, biofilm reactor (dischargeable capacity, film wire radical, operating condition without Technique of Nano Pd
It is all the same) the identical underground water containing nitrate of processing, it is 246mg NO that film surface maximum, which restores flux,3 --N/(m2D),
Water inlet nitrate is 10-20mg NO3 -When-N, water outlet nitrate just cannot be completely removed.Therefore, the biological palladium in embodiment 1 is anti-
It answers device device to be substantially better than original hydrogen-based matter biofilm reactor to the removal effect of nitrate, can be used for containing Pd2+Palladium in waste water
Recycling and its effectively removed applied to oxidative pollutant in actual waste water.
Use structure same as Example 1, biofilm reactor (dischargeable capacity, film wire radical, operating condition without Technique of Nano Pd
It is all the same) the identical simulated wastewater containing chromate of processing, it is 45mg Cr (VI)/(m that film surface maximum, which restores flux,2·
D), when water inlet chromate is 2-10mg Cr (VI), it is discharged chromate poor removal effect.Therefore, the biological palladium in embodiment 1 is anti-
It answers device device to be substantially better than original hydrogen-based matter biofilm reactor to the removal effect of chromate, can be used for practical containing Pd2+Waste water
It the recycling of middle palladium and its is effectively removed applied to oxidative pollutant in actual waste water.
Therefore, structure of the invention is reasonable, high treating effect, and non-porous fine and close hollow-fibre membrane can be used for the system of Technique of Nano Pd
It is standby；Bubble-free aeration can promote the dissolution of gas in water, while H2Infiltration coefficient in the membrane material is known constant, can
Air demand is controlled by adjusting hydrogen partial pressure, hydrogen utilization ratio is improved, avoids H in water2Spilling；High speed return-flow system makes instead
The membrane module upper and lower ends ventilation in device in the state being thoroughly mixed, main reactor is answered, is avoided caused by on-way resistance
Gas diffusion is uneven and utilization rate is low；Auxiliary reactor, which is arranged, can be convenient the acquisition of film wire sample and avoids influencing reactor
Operational effect；The cleaning of film can be completed without dismantling membrane module；Reactor tube body and pipeline have good air-tightness, energy
Accomplish that whole process strictly anaerobic from inlet water to outlet water, anaerobic environment are conducive to biological palladium preparation and provide pollutant removal effect
Fruit；Hydraulically full no head space volume in reactor avoids hydrogen from accumulating and cause the danger of explosion.The present invention can effectively make
Standby biology palladium, and be used for efficiently handling water oxygen contact scar object.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa, which is characterized in that the reactor includes:
Main reactor: it including main reactor tube body (4), is provided at its inner portion along main reactor tube body (4) and is attached with biological palladium
The first non-porous hollow fiber film component (1) and be arranged the first of first non-porous hollow fiber film component (1) upper and lower ends
Hydrogen inlet (3), main reactor tube body (4) the upper end side are equipped with main reactor reflux water out (8), the main reaction
Device tube body (4) lower end side is equipped with main reactor reflux water inlet (7)；
Auxiliary reactor: it including auxiliary reactor tube body (14), is provided at its inner portion along auxiliary reactor tube body (14) and is attached with biology
Second non-porous hollow fiber film component (11) of palladium and setting are the second of second non-porous hollow fiber film component (11) upper end
Hydrogen inlet (13), auxiliary reactor tube body (14) the upper end side are equipped with auxiliary reactor reflux water inlet (10), the other side
Equipped with reactor water outlet (16), auxiliary reactor tube body (14) the lower end side is equipped with auxiliary reactor reflux water out (9), separately
Side is equipped with reactor water inlet (15)；
Main reactor reflux water out (8) is connected with auxiliary reactor reflux water inlet (10), the auxiliary reactor
Reflux water out (9) and main reactor flow back water inlet (7) be connected, first hydrogen inlet (3) and the second hydrogen into
Port (13) is connected with hydrogen source, and the reactor water inlet (15) is connected with water system.
2. a kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa according to claim 1, feature
It is, the first non-porous hollow fiber film component (1) and the second non-porous hollow fiber film component (11) are respectively by complex root
One non-porous hollow fiber film wire (2) and the second non-porous hollow fiber film wire (12) are made, and the first non-porous hollow fiber film wire (2)
Quantity be more than the second non-porous hollow fiber film wire (12).
3. a kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa according to claim 2, feature
It is, the first non-porous hollow fiber film wire (2) is equipped with 50, and the second non-porous hollow fiber film wire (12) is equipped with 10
Root.
4. a kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa according to claim 2, feature
It is, the first non-porous hollow fiber film wire (2) is identical with second non-porous hollow fiber film wire (12), is all made of poly- third
Alkene is made, effective length 27cm, and outer diameter is 200 μm, and internal diameter is 100 μm.
5. a kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa according to claim 1, feature
It is, the first non-porous hollow fiber film component (1) both ends are arranged with hermetically passing main reactor tube body (4) both ends simultaneously respectively
First sleeve (18) with the first hydrogen inlet (3), the second non-porous hollow fiber film component (11) upper end are arranged with
Hermetically passing auxiliary reactor tube body (14) and the second sleeve (19) for having the second hydrogen inlet (13).
6. a kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa according to claim 1 or 5, special
Sign is that the first non-porous hollow fiber film component (1) both ends pass through aperture plastic spiral cover (5) and the main reactor respectively
Tube body (4) is fixed；
The second non-porous hollow fiber film component (11) upper end passes through aperture plastic spiral cover (5) and the auxiliary reactor tube body
(14) upper end is fixed, and the second non-porous hollow fiber film component (11) lower end is fixedly connected with institute by nonporous plastic spiral cover (17)
State auxiliary reactor tube body (14) lower end.
7. a kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa according to claim 6, feature
It is, between the aperture plastic spiral cover (5) and main reactor tube body (4), the aperture plastic spiral cover (5) and auxiliary reactor pipe
Sealing rubber washer (6) are equipped between body (14), between the nonporous plastic spiral cover (17) and auxiliary reactor tube body (14).
8. a kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa according to claim 1, feature
It is, main reactor reflux water out (8) and auxiliary reactor reflux water inlet (10), auxiliary reactor reflux water out (9)
It is connect by hose with main reactor reflux water inlet (7), and flowed back in auxiliary reactor reflux water out (9) and main reactor
Circulating pump (20) are additionally provided between water inlet (7).
9. a kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa according to claim 1, feature
It is, first hydrogen inlet (3) connects external hydrogen gas source by hose connection one with the second hydrogen inlet (13)
Four-way pipe.
10. a kind of hydrogen matrix biopolymers palladium reactor being aerated with non-porous hollow tunica fibrosa according to claim 1, feature
It is, the main reactor tube body (4) and auxiliary reactor tube body (14) are cylinder, and material is quartz glass.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620430A (en) * | 2020-06-04 | 2020-09-04 | 浙江大学 | Hollow fiber membrane reactor based on metal thin film catalysis, manufacturing method and application |
| CN112429844A (en) * | 2020-10-23 | 2021-03-02 | 同济大学 | Method and system for deep denitrification of sewage |
| CN114031171A (en) * | 2021-11-29 | 2022-02-11 | 桂林理工大学 | Hydrogen-based membrane bio-membrane reactor |
| CN114956372A (en) * | 2022-05-09 | 2022-08-30 | 同济大学 | Method and system for realizing rapid degradation of halogenated organic pollutants in water |
| CN115959768A (en) * | 2022-12-29 | 2023-04-14 | 桂林理工大学 | Hydrogen-based membrane bio-membrane reactor system and method for treating 4-bromophenol in tertiary industrial wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003027021A2 (en) * | 2001-09-24 | 2003-04-03 | Malcolm Robert Snowball | Fluid treatment apparatus comprising doped semiconductor material |
| WO2017136528A1 (en) * | 2016-02-03 | 2017-08-10 | Arizona Board Of Regents On Behalf Of Arizona State University | Methods of recovering platinum group metals from waste streams |
-
2018
- 2018-07-10 CN CN201810751816.6A patent/CN108996698A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003027021A2 (en) * | 2001-09-24 | 2003-04-03 | Malcolm Robert Snowball | Fluid treatment apparatus comprising doped semiconductor material |
| WO2017136528A1 (en) * | 2016-02-03 | 2017-08-10 | Arizona Board Of Regents On Behalf Of Arizona State University | Methods of recovering platinum group metals from waste streams |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620430A (en) * | 2020-06-04 | 2020-09-04 | 浙江大学 | Hollow fiber membrane reactor based on metal thin film catalysis, manufacturing method and application |
| CN112429844A (en) * | 2020-10-23 | 2021-03-02 | 同济大学 | Method and system for deep denitrification of sewage |
| CN114031171A (en) * | 2021-11-29 | 2022-02-11 | 桂林理工大学 | Hydrogen-based membrane bio-membrane reactor |
| CN114956372A (en) * | 2022-05-09 | 2022-08-30 | 同济大学 | Method and system for realizing rapid degradation of halogenated organic pollutants in water |
| CN115959768A (en) * | 2022-12-29 | 2023-04-14 | 桂林理工大学 | Hydrogen-based membrane bio-membrane reactor system and method for treating 4-bromophenol in tertiary industrial wastewater |
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Application publication date: 20181214 |