CN106380029B - It is a kind of for the bipolar membrane electrodialysis of waste water deaminizing and the integrating device of hollow fiber membrane contactors and method - Google Patents
It is a kind of for the bipolar membrane electrodialysis of waste water deaminizing and the integrating device of hollow fiber membrane contactors and method Download PDFInfo
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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
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
The invention discloses a kind of for the bipolar membrane electrodialysis of waste water deaminizing and the integrating device of hollow fiber membrane contactors and method, it is characterized in that the sour receiving liquid holding vessel of the acid compartment solution storage tanks of bipolar membrane electrodialysis and hollow fiber membrane contactors is merged, ammonia nitrogen waste liquid is driven into the alkaline chamber in bipolar membrane electrodialysis device by peristaltic pump to carry out adding alkali, improve pH to 11 or so, ammonium ion is set to be converted into the ammonia molecule of free state, the ammonia nitrogen waste liquid after alkali will be added to be introduced into hollow fiber membrane contactors again and carries out deamination, the bronsted lowry acids and bases bronsted lowry that bipolar membrane electrodialysis dissociation salt production may be implemented is supplied in hollow fiber membrane contactors deamination process online, compared with single hollow fiber membrane contactors deamination process, greatly reduce the consumption of chemical reagent, so that ammonia nitrogen separation process is more economically environmentally friendly, it is more suitable for being industrialized It promotes and applies.
Description
Technical field
The invention belongs to ammonia-containing water embrane method deamination technical fields, and in particular to use bipolar membrane electrodialysis and doughnut
The integrated technique of membrane contactor carries out deamination to ammonia nitrogen waste liquid.
Background technique
Ammonia nitrogen is the major pollutants of industrial wastewater and sanitary wastewater, has produced serious dirt to environment and water body
Dye.Therefore, cost-effective control ammonia nitrogen waste water pollution has become the important topic of current environmental worker's research, has obtained industry
The great attention of interior personage.The ammonia nitrogen waste water feature that the factory of different industries goes out with the different plant emissions of the mutually same industry is different
Sample, ammonia nitrogen concentration is also different, and ammonia nitrogen waste water is divided into high concentration (NH according to ammonia-nitrogen content4 +N content be greater than 500mg/L), in
Concentration (NH4 +N content is 50-500mg/L), low concentration (NH4 +N content is less than 50mg/L) three classes.Wastewater with high ammonia nitrogen concentration one
As from the production processes such as coke, ferroalloy, coal gasification, oil refining, animal husbandry, chemical fertilizer, staple fibre and incandescent lamp；In it is dense
Degree ammonia nitrogen waste water is mainly derived from chemical fertilizer, oil refining, glue, synthetic rubber, dairy products production, aviculture, pig breeding industry, papermaking, system
The industry such as leather；Low Concentration Ammonia Containing Wastewater is mainly derived from the numerous food products processing industry such as can, vegetables waste water, paper waste and shallow lake
Powder and cereal processing factory waste water.Currently, both at home and abroad processing ammonia nitrogen waste water technique be roughly divided into physico-chemical process, biological eliminating nitrogen method,
Membrane separation technique.Wherein physico-chemical process includes steam air- extraction, air stripping method, break point chlorination method, selective ion exchange method, urges
Dampness elimination oxidizing process, electrochemical treatment, microwave irradiation, zeolite exchange absorption method and chemical precipitation method (MAP method) etc., biology
Denitrogenation includes biological nitration method, algal culture and immobilization biological method etc..For handling the more mature side of industrial ammonia nitrogen waste water
Method mainly has break point chlorination, selective ion exchange method, air to blow support and vaporizing extract process, bioanalysis, chemical precipitation method and film suction
Receipts method.Wherein, break point chlorination is only suitable for handling Low Concentration Ammonia Containing Wastewater, and can generate secondary pollution；Selective ion exchange
Method needs to reprocess, and technique is more complex；Air stripping and vaporizing extract process are only suitable for handling high-concentration ammonia nitrogenous wastewater, and deamination process by
Temperature influences greatly, to take up a large area；Bioanalysis removal of ammonia and nitrogen is at high cost, and removal efficiency is not high enough；Chemical precipitation method is at high cost；Film is inhaled
Receipts method removal of ammonia and nitrogen has the advantages such as applied widely, removal efficiency is high, at low cost, operation is simple, is more competitive at present
The method for handling ammonia nitrogen waste water.
Chinese patent (CN 104925982 A of 103496817 A, CN and 105130051 A of CN) reports in utilization
Empty fiber membrane contactor recycles the ammonia in ammonia nitrogen waste water by the method that film absorbs.The principle of the method is first to add into ammonia nitrogen waste water
The pH of waste water is adjusted to 10-12 by alkali (NaOH), so that the NH of the free state in waste water4 +Ion conversion is NH3·H2O, thus
Be conducive in film absorption process ammonia molecule and enter sour receiving liquid (such as H through hydrophobic hollow-fibre membrane2SO4), it generates
(NH4)2SO4By-product.The process ammonia nitrogen removal frank is high (ammonia nitrogen removal frank is generally 90% or more), while can be by ammonia in waste liquid
Nitrogen concentration is down to 15mg/L or less.However, membrane absorption method, which need to additionally add a large amount of lye in deamination, adjusts pH, consumption is a large amount of
Strong acid is as sour receiving liquid, and chemical reagent consumption amount is larger, and operating cost is higher.
In embrane method other than film absorption can handle ammonia nitrogen waste water, it is useless that bipolar membrane electrodialysis can also be used for processing ammonia nitrogen
Water.Periodical Water Research 201-209 pages of 89 phase in 2016 reports the ammonium chloride using bipolar membrane electrodialysis from simulation
Hydrochloric acid and ammonium hydroxide are produced in waste water.The technical process is that the ammonium chloride waste-water of simulation is passed through to the salt room of bipolar membrane electrodialysis,
Water under the action of DC electric field among Bipolar Membrane, which can be dissociated, generates H+And OH-Ion.Wherein, H+Ion is through in Bipolar Membrane
Anode membrane layer enter acid compartment, enter the anion Cl of acid compartment with from salt room through anion-exchange membrane-In conjunction with generation hydrochloric acid；OH-From
Son enters alkaline chamber through the cavity block layer in Bipolar Membrane, with the cationic NH for entering alkaline chamber through cation-exchange membrane from salt room4 +Knot
Symphysis is at ammonium hydroxide, to realize the function of producing hydrochloric acid and ammonium hydroxide simultaneously from the ammonium chloride waste-water of simulation.Treatment process master
If being directed to high concentration NH4The dissociation of Cl waste liquid.Other impurity compositions can also be contained in practical waste liquid, such as COD, SO4 2-、Na+, because
This, which directly handles actual waste water using bipolar membrane electrodialysis, cannot produce the higher acid of purity and ammonium hydroxide, this makes Bipolar Membrane electric osmose
Analysis process is lacked competitiveness in directly processing industrial wastewater containing ammonia.In addition, for the ammonia nitrogen waste water of middle low concentration, directly with bipolar
Membrane electrodialysis processing is also less suitably that, because the salt content of waste liquid is lower, conductivity is relatively low, bipolar membrane electrodialysis operation
Process resistance is larger, and energy consumption is higher, and the concentration of the acid and ammonium hydroxide generated is very low, is unfavorable for directly using.
Bipolar membrane electrodialysis can convert salt to bronsted lowry acids and bases bronsted lowry, and membrane absorption method needs to consume greatly when handling ammonia nitrogen waste water
The bronsted lowry acids and bases bronsted lowry of amount, therefore, if can integrate bipolar membrane electrodialysis and hollow fiber membrane contactors, this would be possible to abundant benefit
The advantage absorbed with bipolar membrane electrodialysis process and film improves the efficiency of ammonia nitrogen waste water processing, reduces reagent consumption, from basic
The upper processing cost for reducing ammonia nitrogen waste water.
But it is there is no so far through the integrating device of bipolar membrane electrodialysis and hollow fiber membrane contactors come in removal of ammonia and nitrogen
The report of ammonia in water.
Summary of the invention
The purpose of the present invention is to propose to a kind of bipolar membrane electrodialysis for waste water deaminizing and hollow fiber membrane contactors
Integrating device and method, it is intended to carry out removal of ammonia and nitrogen waste water in conjunction with bipolar membrane electrodialysis and the respective advantage of hollow fiber membrane contactors
In ammonia, to overcome the drawbacks described above of the prior art.
For realize foregoing invention purpose, the present invention adopts the following technical scheme:
Present invention firstly provides the collection of a kind of bipolar membrane electrodialysis for waste water deaminizing and hollow fiber membrane contactors
At device, it is characterized in that:
The integrating device is made of bipolar membrane electrodialysis device and hollow fiber membrane contactors device:
Positive electrode and yin of the bipolar membrane electrodialysis device by membrane stack and by Boards wall in the membrane stack two sides
Electrode is constituted；The membrane stack is after successively alternately being laminated from positive electrode to negative electrode by anode membrane, Bipolar Membrane and cavity block plus runner
Filter and gasket composition, wherein form anode chamber, form alkaline chamber, Bipolar Membrane between anode membrane and Bipolar Membrane between positive electrode and anode membrane
Acid compartment is formed between cavity block, forming salt room between cavity block and anode membrane forms cathode chamber between anode membrane and negative electrode；Pass through sun
Film, Bipolar Membrane and successively replacing for cavity block laminate, and the repetitive unit of " alkaline chamber-acid compartment-salt room " is formed in membrane stack, repeat single
The quantity of member can be one or more.
The anode chamber and cathode chamber are connected by silicone tube, and are connected in electrode solution holding vessel；The salt of the salt room
Room import and the outlet of salt room are connected in salting liquid holding vessel by silicone tube respectively；The alkaline chamber import of the alkaline chamber passes through silica gel
Pipe is connected in ammonia nitrogen waste liquid holding vessel, alkaline chamber outlet by silicone tube be connected to the tube sides of level-one hollow fiber membrane contactors into
Mouthful；The acid compartment import of the acid compartment and acid compartment outlet are connected in sour receiving liquid holding vessel by silicone tube respectively；The positive electricity
Pole passes through the anode and cathode that conducting wire connects DC power supply with negative electrode respectively；Electrode solution holding vessel, salting liquid holding vessel, ammonia nitrogen
The flow that solution in waste liquid holding vessel and sour receiving liquid holding vessel enters in bipolar membrane electrodialysis device passes through electrode chamber respectively
Peristaltic pump, salt room peristaltic pump, alkaline chamber peristaltic pump and the control of acid compartment peristaltic pump；
The hollow fiber membrane contactors device is composed in series by multiple hollow fiber membrane contactors, in which: level-one is hollow
The tube side import of fiber-film contact and the alkaline chamber outlet of bipolar membrane electrodialysis device are connected by silicone tube, the hollow fibre of upper level
The tube side outlet of dimension membrane contactor is connect with the tube side import of next stage hollow fiber membrane contactors, the contact of final stage hollow-fibre membrane
The tube side of device, which is exported, is connected to ammonia nitrogen devil liquor recovery tank by silicone tube and hollow fiber membrane contactors tube side solution dump valve；End
The shell side import of grade hollow fiber membrane contactors is connected to by silicone tube with sour receiving liquid holding vessel, and next stage hollow-fibre membrane connects
The shell-side outlet of tentaculum is connected to the shell side import of upper level hollow fiber membrane contactors by silicone tube, level-one hollow-fibre membrane
The shell-side outlet of contactor is connected to sour receiving liquid holding vessel by silicone tube, to realize in hollow fiber membrane contactors device
The reverse flow of tube side solution and shell side solution；The tube side outlet of final stage hollow fiber membrane contactors passes through silicone tube and hollow fibre
Dimension membrane contactor tube side solution return valve is connected to ammonia nitrogen waste liquid holding vessel；Tube side flow in hollow fiber membrane contactors device
The shell side for passing through the alkaline chamber peristaltic pump and hollow fiber membrane contactors in bipolar membrane electrodialysis device respectively with shell side flow is wriggled
Pump control.
It is using the method that above-mentioned integrating device handles ammonia nitrogen waste liquid:
The 10-90% of electrode solution to electrode solution storage tank volume is first added into electrode solution holding vessel respectively, toward salting liquid
The 10-90% of salting liquid to salting liquid storage tank volume is added in holding vessel, ammonia nitrogen waste liquid is added into ammonia nitrogen waste liquid holding vessel
To the 10-90% of ammonia nitrogen waste liquid storage tank volume, dilute acid soln is added into sour receiving liquid holding vessel to sour receiving liquid holding vessel
The 10-90% of volume；
It is then turned on electrode chamber peristaltic pump, salt room peristaltic pump, alkaline chamber peristaltic pump, acid compartment peristaltic pump, hollow-fibre membrane contact
The shell side peristaltic pump and hollow fiber membrane contactors tube side solution return valve of device respectively store electrode solution holding vessel, salting liquid
Tank, ammonia nitrogen waste liquid holding vessel, the solution in sour receiving liquid holding vessel are recycled to exclude bipolar membrane electrodialysis device and hollow
Bubble in fiber-film contact device；
It is then turned on DC power supply after bubble is drained, and monitors the alkaline chamber exit ammonia of bipolar membrane electrodialysis device by pH meter
The pH value of nitrogen waste liquid adjusts the size of current of DC power supply, so that the pH value of alkaline chamber exit ammonia nitrogen waste liquid is reached desirable value, at this time
Hollow fiber membrane contactors tube side solution dump valve is opened, and closes hollow fiber membrane contactors tube side solution return valve, is passed through
Ammonia nitrogen devil liquor recovery tank receives the waste liquid after deamination, then carries out the processes such as postorder desalination.
Above-mentioned method, feature are lain also in: by adjusting the uninterrupted of alkaline chamber peristaltic pump and the electric current of DC power supply
Size controls the pH value of alkaline chamber exit ammonia nitrogen waste liquid, by changing the concatenated number of hollow fiber membrane contactors controls ammonia
The concentration of ammonia in nitrogen devil liquor recovery tank.
The electrode solution selects the sodium sulphate or sodium nitrate solution of 0.1-1.0mol/L.The salting liquid is 0.5-
The metabisulfite solution of 2.0mol/L.The dilute acid soln is the sulfuric acid solution of 0.05-0.5mol/L.
The pH value of the alkaline chamber exit ammonia nitrogen waste liquid, which reaches desirable value and refers to, reaches 10-12.
The present invention carries out waste water deaminizing using the integrating device of bipolar membrane electrodialysis and hollow fiber membrane contactors, former
Reason is: the ammonia nitrogen waste liquid in ammonia nitrogen waste liquid holding vessel squeezed into the alkaline chamber of bipolar membrane electrodialysis device by alkaline chamber peristaltic pump,
Make to form free state in conjunction with the hydroxide ion generated in the alkaline chamber of the ammonium ion and bipolar membrane electrodialysis in ammonia nitrogen waste liquid
Ammonia molecule, then the ammonia nitrogen waste liquid that pH value reaches 10-12 after alkali will be added to be introduced into the tube side of hollow fiber membrane contactors, pass through
The shell side peristaltic pump of hollow fiber membrane contactors squeezes into sour receiving liquid into the shell side of hollow fiber membrane contactors, so that ammonia
The ammonia molecule of free state is penetrated into from the shell side of hollow fiber membrane contactors by hydrophobic hollow-fibre membrane in nitrogen waste liquid
In tube side, ammonium ion is formed in conjunction with the hydrogen ion in tube side, realizes the recycling of ammonia in waste water；Meanwhile bipolar membrane electrodialysis
Device can constantly provide acid into sour receiving liquid holding vessel, provide hydrogen ion online for recycling ammonia process.Therefore, by Bipolar Membrane electricity
Electrodialysis apparatus and hollow fiber membrane contactors device are integrated, and bipolar membrane electrodialysis may be implemented as hollow fiber membrane contactors recycling
Ammonia process provides bronsted lowry acids and bases bronsted lowry online, reduces the consumption of chemical reagent.
Compared with the prior art, the beneficial effects of the present invention are embodied in:
The integrating device of bipolar membrane electrodialysis and hollow fiber membrane contactors is applied to ammonia nitrogen waste water for the first time by the present invention
Deamination process, with Chinese patent (CN 104925982 A of 103496817 A, CN and 105130051 A of CN) with single hollow
Fiber-film contact deamination process is compared, and the consumption of chemical reagent (bronsted lowry acids and bases bronsted lowry) is greatly reduced, it is only necessary to be provided for bipolar
The salt of membrane electrodialysis dissociation and consume certain electricity charge, so that it may for ammonia nitrogen waste water deamination process realize provide online alkali and
Acid reduces operating cost, and entire deamination process is environmentally protective.With periodical Water Research 89 phase 201- in 2016
The hydrochloric acid that produced from the ammonium chloride waste-water of simulation using bipolar membrane electrodialysis of the reports of page 209 is compared with ammonium hydroxide, Bipolar Membrane electric osmose
The integrating device of analysis and hollow fiber membrane contactors is used to not only processing ammonium chloride waste-water, could be applicable to handle while containing ammonium
The complicated solution of radical ion and other inorganic salts, is more suitable for industrial applications；In addition, bipolar membrane electrodialysis connects with hollow-fibre membrane
The not traditional intermittent operation of the integrating device and method of tentaculum, it is integrated operation, it can be achieved that ammonia nitrogen waste water it is continuous
Change processing provides new approaches for industrialization continuous production.
Detailed description of the invention
Fig. 1 is the integrating device of bipolar membrane electrodialysis and hollow fiber membrane contactors；
Fig. 2 is the membrane stack layout viewing in bipolar membrane electrodialysis；
Figure label: 1 bipolar membrane electrodialysis device；2 membrane stacks；2-1 negative electrode；2-2 positive electrode；2-3 cathode chamber inlet；2-
4 cathode chamber outlets；The import of the anode chamber 2-5；2-6 anode compartment outlet；The room import of 2-7 salt；The outlet of 2-8 salt room；2-9 alkaline chamber import；
The outlet of 2-10 alkaline chamber；2-11 acid compartment import；The outlet of 2-12 acid compartment；3 DC power supplies；4 electrode solution holding vessels；5 salting liquid holding vessels；
6 ammonia nitrogen waste liquid holding vessels；7 sour receiving liquid holding vessels；8 ammonia nitrogen devil liquor recovery tanks；9 electrode chamber peristaltic pumps；10 salt room peristaltic pumps；11
Alkaline chamber peristaltic pump；12 acid compartment peristaltic pumps；The shell side peristaltic pump of 13 hollow fiber membrane contactors；The contact of 14 level-one hollow-fibre membranes
Device；The tube side import of 14-1 level-one hollow fiber membrane contactors；The tube side of 14-2 level-one hollow fiber membrane contactors exports；14-3
The shell side import of level-one hollow fiber membrane contactors；The shell-side outlet of 14-4 level-one hollow fiber membrane contactors；15 second levels are hollow
Fiber-film contact；The tube side import of 15-1 second level hollow fiber membrane contactors；The pipe of 15-2 second level hollow fiber membrane contactors
Journey outlet；The shell side import of 15-3 second level hollow fiber membrane contactors；The shell-side outlet of 15-4 second level hollow fiber membrane contactors；
16 final stage hollow fiber membrane contactors；The tube side import of 16-1 final stage hollow fiber membrane contactors；16-2 final stage hollow-fibre membrane
The tube side of contactor exports；The shell side import of 16-3 final stage hollow fiber membrane contactors；16-4 final stage hollow fiber membrane contactors
Shell-side outlet；17pH meter；18 hollow fiber membrane contactors tube side solution return valves；19 hollow fiber membrane contactors tube side solution
Dump valve.
Specific embodiment
The method of present invention be described in more detail by the following examples waste water deaminizing.
Embodiment 1
As shown in Figure 1, the present embodiment is for the bipolar membrane electrodialysis of waste water deaminizing and integrating for hollow fiber membrane contactors
Device is made of bipolar membrane electrodialysis device 1 and hollow fiber membrane contactors device:
Positive electrode 2-2 and negative electrode of the bipolar membrane electrodialysis device 1 by membrane stack 2 and by Boards wall in membrane stack two sides
2-1 is constituted.As shown in Fig. 2, membrane stack is successively alternately to be laminated by anode membrane, Bipolar Membrane and cavity block from positive electrode 2-2 to negative electrode 2-1
It is formed afterwards plus runner filter and gasket, wherein forms anode chamber between positive electrode 2-2 and anode membrane, shape between anode membrane and Bipolar Membrane
At alkaline chamber, acid compartment is formed between Bipolar Membrane and cavity block, forming salt room between cavity block and anode membrane, shape between anode membrane and negative electrode 2-1
At cathode chamber；
Anode chamber and cathode chamber (cathode chamber inlet 2-3, cathode chamber outlet 2-4, anode chamber's import 2-5, anode compartment outlet 2-
6) it is connected, and is connected in electrode solution holding vessel 4 by silicone tube；The salt room import 2-7 of salt room and salt room outlet 2-8 lead to respectively
Silicone tube is crossed to be connected in salting liquid holding vessel 5；The alkaline chamber import 2-9 of alkaline chamber is connected to ammonia nitrogen waste liquid holding vessel by silicone tube
In 6, the alkaline chamber outlet 2-10 of alkaline chamber is connected to the tube side import 14-1 of level-one hollow fiber membrane contactors by silicone tube；Acid compartment
Acid compartment import 2-11 and acid compartment outlet 2-12 pass through silicone tube respectively and be connected in sour receiving liquid holding vessel 7；Electrode solution storage
Solution in tank 4, salting liquid holding vessel 5, ammonia nitrogen waste liquid holding vessel 6 and sour receiving liquid holding vessel 7 enters bipolar membrane electrodialysis dress
It sets the flow in 1 and passes through electrode chamber peristaltic pump 9, salt room peristaltic pump 10, alkaline chamber peristaltic pump 11 and the control of acid compartment peristaltic pump 12 respectively；
Positive electrode 2-2 passes through the anode and cathode that conducting wire connects DC power supply 3 with negative electrode 2-1 respectively.
Anode membrane used is the CMX film (3) of Astom company, Japan production in the present embodiment, and cavity block is Astom company, Japan
The AMX film (2) of production, Bipolar Membrane are the BP-1E film (2) of Astom company, Japan production, and effective membrane area of every film is
189cm2, spacer thickness 0.8mm.
Hollow fiber membrane contactors device is connected in series by multiple hollow fiber membrane contactors, as shown, by level-one
Empty fiber membrane contactor 14, second level hollow fiber membrane contactors 15 ..., final stage hollow fiber membrane contactors 16 are connected in series；
Wherein: the tube side import 14-1 of level-one hollow fiber membrane contactors and the alkaline chamber outlet 2-10 of bipolar membrane electrodialysis device pass through silicon
Sebific duct connection, the tube side outlet of upper level hollow fiber membrane contactors and the tube side import of next stage hollow fiber membrane contactors connect
It connects, the tube side outlet 16-2 of final stage hollow fiber membrane contactors is discharged by silicone tube and hollow fiber membrane contactors tube side solution
Valve 19 is connected to ammonia nitrogen devil liquor recovery tank 8；The shell side import 16-3 of final stage hollow fiber membrane contactors is connect by silicone tube and acid
It receives liquid holding vessel 7 to be connected to, the shell-side outlet of next stage hollow fiber membrane contactors and the shell of upper level hollow fiber membrane contactors
Journey import is connected to by silicone tube, and the shell-side outlet 14-4 of level-one hollow fiber membrane contactors is connected to sour reception by silicone tube
Liquid holding vessel 7, to realize the reverse flow of tube side solution and shell side solution in hollow fiber membrane contactors device；Final stage is hollow
The tube side outlet 16-2 of fiber-film contact is connected to by silicone tube and hollow fiber membrane contactors tube side solution return valve 18
Ammonia nitrogen waste liquid holding vessel 6；Tube side flow and shell side flow in hollow fiber membrane contactors device pass through Bipolar Membrane electric osmose respectively
The shell side peristaltic pump 13 of alkaline chamber peristaltic pump 11 and hollow fiber membrane contactors in analysis apparatus 1 controls.
Specifically, the concatenated number of the present embodiment hollow fiber membrane contactors is 4, hollow fiber membrane contactors are Zhejiang
The hydrophobic PTFE hollow fiber membrane contactors of eastern overall situation Engineering Co., Ltd production.Film wire mean inside diameter is 1.2mm, average outer
Diameter is 2.25mm, the long 40cm of every film wire, and 100 film wires, total effective contact area are contained in each hollow fiber membrane contactors
For 0.28m2。
Embodiment 2
When being handled using the bipolar membrane electrodialysis device in the integrating device of embodiment 1 ammonia nitrogen waste liquid, first toward 1L
The metabisulfite solution of 0.5L 0.3mol/L is added in electrode solution holding vessel 4；0.8L is added into 1L salting liquid holding vessel 5
The metabisulfite solution of 1.0mol/L；The certain density simulation ammonia nitrogen waste liquid of 8L is added into 10L ammonia nitrogen waste liquid holding vessel 6 (to contain
There are the sodium chloride of 2000mg/L and the sodium sulphate of 2000mg/L)；1.5L 0.3mol/L is added into 2L acid receiving liquid holding vessel 7
Sulfuric acid solution.
Open electrode chamber peristaltic pump 9 (0.3L/min), salt room peristaltic pump 10 (0.3L/min), alkaline chamber peristaltic pump 11, acid compartment
Peristaltic pump 12 (0.3L/min), hollow fiber membrane contactors tube side solution return valve 18, it is molten to electrode solution holding vessel 4, salt respectively
Liquid holding vessel 5, ammonia nitrogen waste liquid holding vessel 6, the solution in sour receiving liquid holding vessel 7 are recycled to exclude bipolar membrane electrodialysis dress
Set the bubble in 1.
It is then turned on DC power supply 3 after bubble is drained, and monitors the alkaline chamber outlet of bipolar membrane electrodialysis device by pH meter 17
The pH value of ammonia nitrogen waste liquid at 2-10 adjusts the size of current of DC power supply 3, reaches the pH value of ammonia nitrogen waste liquid at alkaline chamber outlet 2-10
To 10-12.
The present embodiment has investigated that (0.034,0.068,0.102L/min, correspondence are hollow in certain alkaline chamber wriggling pump discharge
Fiber-film contact tube side line flow velocity is respectively 0.5,1,1.5cm/s) under, the ammonia nitrogen waste liquid (NH of various concentration4 +- N concentration is
200,400,600,800,1000mg/L) current density that consumes is needed, it is changed further according to electric current, effective membrane area and mass flow
Standardization current density is calculated, experimental result is as shown in table 1.
Current density, standardization current density and alkaline chamber under the conditions of 1. different operation of table export pH
Wherein, current density (i is standardizedStandardization, mA/ (cm2Mg/min calculation formula)) are as follows:
iStandardization=I/ (CQA)
In formula, C is NH in ammonia nitrogen waste liquid4 +The concentration of-N, Q are alkaline chamber peristaltic pump uninterrupted, and A is the significant surface of single film
Product, I is size of current.
As known from Table 1, with the increase of ammonia nitrogen concentration and alkaline chamber wriggling pump discharge in ammonia nitrogen waste liquid, bipolar membrane electrodialysis institute
The current density needed gradually increases, and required standardization current density does not have significant change.From the experimental results, it standardizes
Current density increases with the increase of pH, and substantially in a linear relationship, experimental repeatability is preferable.By linear fit it is found that working as
When the pH value for controlling the alkaline chamber exit ammonia nitrogen waste liquid of bipolar membrane electrodialysis device is 10.5-11.5, needed for bipolar membrane electrodialysis
Standardization current density be 0.26-0.33mA/ (cm2Mg/min), this can provide important operation to industrialized production
Parameter guidance, can convert according to actual flow and concentration, immediately arrive at size of current required for bipolar membrane electrodialysis.
Embodiment 3
When using handling in the integrating device of embodiment 1 ammonia nitrogen waste liquid, first it is added into 1L electrode solution holding vessel 4
The metabisulfite solution of 0.5L 0.3mol/L；The metabisulfite solution of 0.8L 1.0mol/L is added into 1L salting liquid holding vessel 5；It is past
In 10L ammonia nitrogen waste liquid holding vessel 6 be added the certain density simulation ammonia nitrogen waste liquid of 8L (the sodium chloride containing 2000mg/L with
The sodium sulphate of 2000mg/L)；The sulfuric acid solution of 1.5L 0.3mol/L is added into 2L acid receiving liquid holding vessel 7.
Open electrode chamber peristaltic pump 9 (0.3L/min), salt room peristaltic pump 10 (0.3L/min), alkaline chamber peristaltic pump 11
The shell side peristaltic pump 13 and doughnut of (0.034L/min), acid compartment peristaltic pump 12 (0.3L/min), hollow fiber membrane contactors
Membrane contactor tube side solution return valve 18, respectively to electrode solution holding vessel 4, salting liquid holding vessel 5, ammonia nitrogen waste liquid holding vessel 6, acid
Solution in receiving liquid holding vessel 7 is recycled to exclude in bipolar membrane electrodialysis device 1 and hollow fiber membrane contactors device
Bubble.
It is then turned on DC power supply 3 after bubble is drained, and monitors the alkaline chamber outlet of bipolar membrane electrodialysis device by pH meter 17
The pH value of ammonia nitrogen waste liquid at 2-10 adjusts the size of current of DC power supply 3, reaches the pH value of ammonia nitrogen waste liquid in alkaline chamber outlet 2-10
To 11 ± 0.1, hollow fiber membrane contactors tube side solution dump valve 19 is then opened, and close hollow fiber membrane contactors tube side
Solution return valve 18, the waste liquid after deamination is received by ammonia nitrogen devil liquor recovery tank 8.
In the present embodiment, the concatenated number of hollow fiber membrane contactors is 4, and it is hollow that deamination process monitors every level-one respectively
The concentration of ammonia nitrogen, and calculates ammonia removal rate in the outlet of fiber-film contact tube side, every group experiment parallel testing 3 times, ammonia nitrogen removal
Rate average value is as shown in table 2.
The ammonia of the integrating device of 2. bipolar membrane electrodialysis of table and hollow fiber membrane contactors processing various concentration ammonia nitrogen waste liquid
Nitrogen removal efficiency
As known from Table 2, with the increase of ammonia nitrogen concentration in waste liquid, ammonia-nitrogen removal rate is in downward trend on the whole, when dense
After degree increases to 800mg/L, ammonia-nitrogen removal rate there is no significant change, this illustrates that hollow fiber membrane contactors processing is high
Ammonia nitrogen removal fast speed when concentration ammonia nitrogen waste liquid.Under a certain concentration, with the increase of hollow fiber membrane contactors series, ammonia
Nitrogen removal efficiency is in being gradually increasing trend, and after level Four, ammonia-nitrogen removal rate may be up to 55.4-65.2%, behind can pass through increase
The series of hollow fiber membrane contactors further increases ammonia-nitrogen removal rate to 90% or even 99% or more.
In short, the integrating device of bipolar membrane electrodialysis and hollow fiber membrane contactors when handling ammonia nitrogen waste water, it can be achieved that
Online to provide soda acid, continuous production greatly reduces chemistry compared with single hollow fiber membrane contactors handle ammonia nitrogen waste water
The consumption of reagent is more suitable for carrying out industrial application so that ammonia nitrogen separation process is more economically environmentally friendly.
Claims (7)
1. a kind of for the bipolar membrane electrodialysis of waste water deaminizing and the integrating device of hollow fiber membrane contactors, it is characterised in that:
The integrating device is made of bipolar membrane electrodialysis device (1) and hollow fiber membrane contactors device:
Positive electrode (2- of the bipolar membrane electrodialysis device (1) by membrane stack (2) and by Boards wall in the membrane stack two sides
2) it is constituted with negative electrode (2-1)；The membrane stack be by anode membrane, Bipolar Membrane and cavity block from positive electrode (2-2) to negative electrode (2-1) according to
Secondary alternating forms after laminating plus runner filter and gasket, and adjacent with positive electrode and negative electrode is all anode membrane；Wherein positive electricity
Anode chamber is formed between pole (2-2) and anode membrane adjacent thereto, forms cathode between negative electrode (2-1) and anode membrane adjacent thereto
Room forms alkaline chamber between adjacent anode membrane and Bipolar Membrane, form acid compartment between adjacent Bipolar Membrane and cavity block, adjacent cavity block and
Forming salt room between anode membrane；
The anode chamber and cathode chamber are connected by silicone tube, and are connected in electrode solution holding vessel (4)；The salt room of the salt room
Import (2-7) and salt room outlet (2-8) are connected in salting liquid holding vessel (5) by silicone tube respectively；The alkaline chamber of the alkaline chamber
Import (2-9) is connected in ammonia nitrogen waste liquid holding vessel (6) by silicone tube, and alkaline chamber exports (2-10) and is connected to one by silicone tube
The tube side import (14-1) of grade hollow fiber membrane contactors；The acid compartment import (2-11) of the acid compartment and acid compartment outlet (2-12) point
It is not connected in sour receiving liquid holding vessel (7) by silicone tube；The positive electrode (2-2) and negative electrode (2-1) are respectively by leading
Line connects the anode and cathode of DC power supply (3)；Electrode solution holding vessel (4), salting liquid holding vessel (5), ammonia nitrogen waste liquid holding vessel
(6) and the flow that enters in bipolar membrane electrodialysis device (1) of the solution in sour receiving liquid holding vessel (7) to pass through electrode chamber respectively compacted
Dynamic pump (9), salt room peristaltic pump (10), alkaline chamber peristaltic pump (11) and acid compartment peristaltic pump (12) control；
The hollow fiber membrane contactors device is connected in series by multiple hollow fiber membrane contactors, in which: level-one doughnut
The tube side import (14-1) of membrane contactor is connect with the alkaline chamber of bipolar membrane electrodialysis device outlet (2-10) by silicone tube, and upper one
The tube side outlet of grade hollow fiber membrane contactors is connect with the tube side import of next stage hollow fiber membrane contactors, the hollow fibre of final stage
The tube side outlet (16-2) of dimension membrane contactor is connected to by silicone tube with hollow fiber membrane contactors tube side solution dump valve (19)
In ammonia nitrogen devil liquor recovery tank (8)；The shell side import (16-3) of final stage hollow fiber membrane contactors passes through silicone tube and sour receiving liquid
Holding vessel (7) connection, the shell-side outlet of next stage hollow fiber membrane contactors and the shell side of upper level hollow fiber membrane contactors
Import is connected to by silicone tube, and the shell-side outlet (14-4) of level-one hollow fiber membrane contactors is connected to sour reception by silicone tube
Liquid holding vessel (7), to realize the reverse flow of tube side solution and shell side solution in hollow fiber membrane contactors device；In final stage
The tube side outlet (16-2) of empty fiber membrane contactor passes through silicone tube and hollow fiber membrane contactors tube side solution return valve (18)
It is connected to ammonia nitrogen waste liquid holding vessel (6)；Tube side flow and shell side flow in the hollow fiber membrane contactors device lead to respectively
Cross shell side peristaltic pump (13) control of the alkaline chamber peristaltic pump (11) and hollow fiber membrane contactors in bipolar membrane electrodialysis device (1)
System.
2. the method handled using integrating device described in claim 1 ammonia nitrogen waste liquid, it is characterised in that:
The 10-90% of electrode solution to electrode solution storage tank volume is first added into electrode solution holding vessel (4) respectively, is stored up toward salting liquid
The 10-90% that salting liquid to salting liquid storage tank volume is added in tank (5) is deposited, ammonia nitrogen is added into ammonia nitrogen waste liquid holding vessel (6)
Dilute acid soln is added into sour receiving liquid holding vessel (7) to sour receiving liquid to the 10-90% of ammonia nitrogen waste liquid storage tank volume for waste liquid
Store the 10-90% of tank volume；
It is then turned on electrode chamber peristaltic pump (9), salt room peristaltic pump (10), alkaline chamber peristaltic pump (11), acid compartment peristaltic pump (12), hollow
The shell side peristaltic pump (13) and hollow fiber membrane contactors tube side solution return valve (18) of fiber-film contact, respectively to electrode solution
Holding vessel (4), salting liquid holding vessel (5), ammonia nitrogen waste liquid holding vessel (6), the solution in sour receiving liquid holding vessel (7) are recycled
To exclude the bubble in bipolar membrane electrodialysis device (1) and hollow fiber membrane contactors device；
It is then turned on after bubble is drained DC power supply (3), and monitors the alkaline chamber outlet of bipolar membrane electrodialysis device by pH meter (17)
The pH value of ammonia nitrogen waste liquid at (2-10), adjusts the size of current of DC power supply, makes the pH of ammonia nitrogen waste liquid at alkaline chamber outlet (2-10)
Value reaches desirable value, then opens hollow fiber membrane contactors tube side solution dump valve (19), and closes hollow-fibre membrane contact
Device tube side solution return valve (18), the waste liquid after deamination is received by ammonia nitrogen devil liquor recovery tank (8).
3. method according to claim 2, it is characterised in that: by the uninterrupted and direct current that adjust alkaline chamber peristaltic pump (11)
The size of current of power supply (3) passes through to control the pH value that alkaline chamber exports ammonia nitrogen waste liquid at (2-10) and changes hollow-fibre membrane contact
The concatenated number of device controls the concentration of ammonia in ammonia nitrogen devil liquor recovery tank (8).
4. method according to claim 2, it is characterised in that: the electrode solution is the sodium sulphate or nitric acid of 0.1-1.0mol/L
Sodium solution.
5. method according to claim 2, it is characterised in that: the salting liquid is the metabisulfite solution of 0.5-2.0mol/L.
6. method according to claim 2, it is characterised in that: the dilute acid soln is the sulfuric acid solution of 0.05-0.5mol/L.
7. method according to claim 2, it is characterised in that: the pH value of ammonia nitrogen waste liquid reaches at the alkaline chamber outlet (2-10)
Desirable value, which refers to, reaches 10-12.
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| CN107055712B (en) * | 2017-05-05 | 2020-06-05 | 合肥工业大学 | Method for recovering ammonia nitrogen, phosphorus and volatile fatty acid in livestock and poultry excrement hydrolysate by using two-stage bipolar membrane electrodialysis |
| EP3717409B1 (en) * | 2017-11-27 | 2022-03-16 | Universiteit Gent | Method for recovering n from a liquid waste stream |
| CN111655629A (en) * | 2017-12-04 | 2020-09-11 | 新南创新有限公司 | Ammonia nitrogen recovery equipment and method |
| CN110902895A (en) * | 2019-10-31 | 2020-03-24 | 重庆大学 | Electrochemical membrane separation method for removing and recovering ammonia nitrogen in landfill leachate |
| CN113816542B (en) * | 2021-10-26 | 2023-04-18 | 福建船政交通职业学院 | Electrochemical system and method for recycling ammonia nitrogen and rare earth ions in low-concentration rare earth wastewater |
| CN115385496A (en) * | 2022-08-29 | 2022-11-25 | 中触媒新材料股份有限公司 | Recovery system and method for waste liquid produced by ammonium nitrate exchange molecular sieve |
| CN116185087A (en) * | 2023-05-04 | 2023-05-30 | 科大智能物联技术股份有限公司 | Closed-loop deamination control system based on machine learning |
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| CN102515317A (en) * | 2012-01-10 | 2012-06-27 | 刘景亮 | Method and device for producing acid and ammonia water by using ammonia-nitrogen waste water |
| CN105671587A (en) * | 2015-12-10 | 2016-06-15 | 浙江工业大学 | Method and device for preparing methionine and recovering by-product-carbon dioxide |
| CN105712560A (en) * | 2016-04-13 | 2016-06-29 | 北京新源国能科技集团股份有限公司 | Device and method for treating high-salinity wastewater with forward osmosis technique |
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| CN102515317A (en) * | 2012-01-10 | 2012-06-27 | 刘景亮 | Method and device for producing acid and ammonia water by using ammonia-nitrogen waste water |
| CN105671587A (en) * | 2015-12-10 | 2016-06-15 | 浙江工业大学 | Method and device for preparing methionine and recovering by-product-carbon dioxide |
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