CN115490308A - Reverse osmosis concentrated water regeneration treatment equipment and method - Google Patents
Reverse osmosis concentrated water regeneration treatment equipment and method Download PDFInfo
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- CN115490308A CN115490308A CN202211306631.7A CN202211306631A CN115490308A CN 115490308 A CN115490308 A CN 115490308A CN 202211306631 A CN202211306631 A CN 202211306631A CN 115490308 A CN115490308 A CN 115490308A
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- phosphorus
- reverse osmosis
- concentrated water
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- osmosis concentrated
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 87
- 230000008929 regeneration Effects 0.000 title claims abstract description 43
- 238000011069 regeneration method Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 178
- 239000011574 phosphorus Substances 0.000 claims abstract description 178
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 176
- 239000003513 alkali Substances 0.000 claims abstract description 112
- 239000012528 membrane Substances 0.000 claims abstract description 88
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 229910052742 iron Inorganic materials 0.000 claims abstract description 35
- 238000011033 desalting Methods 0.000 claims abstract description 26
- 238000010612 desalination reaction Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 37
- 238000005191 phase separation Methods 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 19
- -1 hydroxide ions Chemical class 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- 230000008878 coupling Effects 0.000 claims description 13
- 238000010168 coupling process Methods 0.000 claims description 13
- 238000005859 coupling reaction Methods 0.000 claims description 13
- 230000009471 action Effects 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 238000005341 cation exchange Methods 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000005349 anion exchange Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 description 6
- 239000010802 sludge Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009294 enhanced biological phosphorus removal Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 229910052567 struvite Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/4604—Treatment of water, waste water, or sewage by electrochemical methods for desalination of seawater or brackish water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- 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
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
-
- 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
- C02F2101/105—Phosphorus compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The application relates to the field of water treatment equipment, in particular to reverse osmosis concentrated water regeneration treatment equipment and method. The reverse osmosis concentrated water regeneration treatment equipment comprises a reaction tank, a membrane component, an anode plate, a cathode plate, a phosphorus drawing tube group and an alkali liquor tube group; the membrane assembly, the anode plate and the cathode plate are all arranged in the reaction tank, and the membrane assembly divides the reaction tank into a phosphorus concentration chamber, a desalting chamber and an alkali chamber; the phosphorus draw tube group is used for leading out phosphorus draw solution in the phosphorus concentration chamber, and leading the phosphorus draw solution into the phosphorus concentration chamber after separating iron cyanite in the phosphorus draw solution; the alkali liquor pipe group is used for introducing alkali liquor into the alkali chamber. The reverse osmosis concentrated water regeneration treatment equipment can carry out regeneration treatment on reverse osmosis concentrated water, and can carry out resource and energy recovery to the maximum extent while ensuring the desalination effect on the reverse osmosis concentrated water; wherein, when the phosphorus in the reverse osmosis concentrated water is to be recovered, high value-added vivianite can be formed.
Description
Technical Field
The application relates to the field of water treatment equipment, in particular to reverse osmosis concentrated water regeneration treatment equipment and method.
Background
At present, in order to respond to the continuous improvement of the utilization rate of municipal reclaimed water, save water resources and expand the use application of the reclaimed water, an ultrafiltration-reverse osmosis combined process is used as a production process unit of conventional high-quality reclaimed water. However, phosphorus is a main pollutant causing eutrophication of water bodies, and is an increasingly scarce non-renewable resource; with the increase of the demand of phosphorus resources and the increase of the exploitation amount, the rich phosphorus ore is exploited for almost the expected decades, the traditional phosphorus removal concept in water treatment is changed into phosphorus recovery, and the phosphorus recovery from reverse osmosis concentrated water and sludge containing rich phosphorus resources is imperative.
Disclosure of Invention
The application provides a reverse osmosis concentrated water regeneration treatment device and method, which aim to improve the problems.
The invention is particularly such that:
a reverse osmosis concentrated water regeneration treatment device comprises a reaction tank, a membrane component, an anode plate, a cathode plate, a phosphorus dip tube group and an alkali liquor tube group;
the membrane assembly, the anode plate and the cathode plate are all arranged in the reaction tank, the reaction tank is divided into a phosphorus concentration chamber, a desalting chamber and an alkali chamber by the membrane assembly, and the phosphorus concentration chamber, the desalting chamber and the alkali chamber are all positioned between the anode plate and the cathode plate; the reaction tank is provided with an electrode liquid circulating injection port, a reverse osmosis concentrated water inlet and a regenerated water outlet, and the electrode liquid circulating injection port is used for introducing electrode liquid into the reaction tank; the reverse osmosis concentrated water enters the desalting chamber from a reverse osmosis concentrated water inlet and is led out from a regenerated water outlet;
the phosphorus drawing pipe group and the alkali liquor pipe group are both communicated with the reaction tank; the phosphorus draw tube group is used for leading out phosphorus draw solution in the phosphorus concentration chamber, and leading the phosphorus draw solution into the phosphorus concentration chamber after separating iron cyanite in the phosphorus draw solution; the alkali liquor pipe group is used for introducing alkali liquor into the alkali chamber.
In one embodiment of the invention, the phosphorus dip tube group comprises a phosphorus dip liquid circulating tube, a phosphorus circulating pump, a three-phase separation tank and a gas storage tank;
both ends of the phosphorus drawing liquid circulating pipe are communicated with the phosphorus concentration chamber, and the phosphorus circulating pump and the three-phase separation tank are communicated with the phosphorus drawing liquid circulating pipe; the phosphorus drawing liquid circulating pipe is used for guiding the phosphorus drawing liquid in the phosphorus concentration chamber into the three-phase separation tank under the action of the phosphorus circulating pump; the three-phase separation tank is used for separating hydrogen and vivianite crystals from the phosphorus drawing liquid, and the separated phosphorus drawing liquid is led into the phosphorus concentration chamber through a phosphorus drawing liquid circulating pipe;
the gas storage tank is communicated with the three-phase separation tank and is used for storing the separated hydrogen.
In one embodiment of the present invention, a three-phase separator for separating hydrogen from the phosphorus draw solution is built in an upper end of the three-phase separation tank, and a tapered portion for collecting the vivianite is provided in a lower end of the three-phase separation tank.
In one embodiment of the invention, the alkali liquor pipe group comprises an alkali liquor circulating pipe, an alkali liquor tank and an alkali liquor circulating pump;
both ends of the alkali liquor circulating pipe are communicated with the alkali chamber, and the alkali liquor tank and the alkali liquor circulating pump are communicated with the alkali liquor circulating pipe;
the alkali liquor circulating pipe is used for guiding the alkali liquor in the alkali liquor tank into the alkali chamber under the action of the alkali liquor circulating pump.
In one embodiment of the invention, the membrane component comprises an iron net coupling bipolar membrane, a cathode membrane, an anode membrane and a bipolar membrane, wherein the bipolar membrane, the cathode membrane, the anode membrane and the bipolar membrane are sequentially arranged at intervals in the direction from the anode plate to the cathode plate, the phosphorus concentration chamber is positioned between the iron net coupling bipolar membrane and the cathode membrane, the desalination chamber is positioned between the cathode membrane and the anode membrane, and the alkali chamber is positioned between the anode membrane and the bipolar membrane or between the anode membrane and the iron net coupling bipolar membrane.
In one embodiment of the invention, the surface of the cation exchange layer of the iron net coupled bipolar membrane is loaded with a layer of iron net with a rhombus structure, and the thickness of the iron net is 0.125mm-0.25mm.
A reverse osmosis concentrated water regeneration treatment method is realized by adopting the reverse osmosis concentrated water regeneration treatment equipment, and comprises the following steps:
the reverse osmosis concentrated water is led into a desalting chamber in the reaction tank through a reverse osmosis concentrated water inlet, under the action of an external voltage, cations enter an alkali chamber through an anode membrane, phosphate ions enter a phosphorus concentration chamber through a cathode membrane, and desalted regenerated water is discharged through a regenerated water outlet;
the alkali chamber is low-concentration sodium hydroxide, and the concentration of alkali liquor in the alkali chamber is increased along with the increase of hydroxide ions generated by the transferred cations and an anion exchange layer in the bipolar membrane;
a low-concentration phosphate solution is arranged in the phosphorus concentration chamber, hydrogen ions generated by a cation exchange layer in the bipolar membrane partially react with an iron net to generate ferrous ions and hydrogen, and the iron ions and the transferred phosphate ions generate a vivianite crystal;
the phosphorus draw solution flowing out of the phosphorus concentration chamber comprises a vivianite crystal, hydrogen and phosphoric acid, the separated hydrogen is guided into the gas storage tank for storage through separation of the three-phase separation tank, the separated vivianite crystal is gradually separated out at the bottom end of the three-phase separation tank to generate vivianite, and the separated phosphorus draw solution circulates into the phosphorus concentration chamber again.
In one embodiment of the invention, the applied voltage of the reaction cell is 1.1-1.5V.
In one embodiment of the invention, the flow rates of the reverse osmosis concentrated water, the alkali liquor and the phosphorus draw solution are all 35-50L/h.
In one embodiment of the invention, the alkali liquor is sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.02-0.05mol/L;
the phosphorus extraction solution is phosphate solution, and the concentration of the phosphate solution is 0.02-0.05mol/L.
The beneficial effects of the invention are that:
the reverse osmosis concentrated water regeneration treatment equipment comprises a reaction tank, a membrane component, an anode plate, a cathode plate, a phosphorus dip tube group and an alkali liquor tube group; the membrane assembly, the anode plate and the cathode plate are all arranged in the reaction tank, the reaction tank is divided into a phosphorus concentration chamber, a desalting chamber and an alkali chamber by the membrane assembly, and the phosphorus concentration chamber, the desalting chamber and the alkali chamber are all positioned between the anode plate and the cathode plate; the reaction tank is provided with an electrode liquid circulating injection port, a reverse osmosis concentrated water inlet and a regenerated water outlet, and the electrode liquid circulating injection port is used for introducing electrode liquid into the reaction tank; the reverse osmosis concentrated water enters the desalting chamber from a reverse osmosis concentrated water inlet and is led out from a regenerated water outlet; the phosphorus drawing pipe group and the alkali liquor pipe group are both communicated with the reaction tank; the phosphorus draw tube group is used for leading out phosphorus draw solution in the phosphorus concentration chamber, and leading the phosphorus draw solution into the phosphorus concentration chamber after separating iron cyanite in the phosphorus draw solution; the alkali liquor pipe group is used for introducing alkali liquor into the alkali chamber. The reverse osmosis concentrated water regeneration treatment equipment can carry out regeneration treatment on reverse osmosis concentrated water, and can carry out resource and energy recovery to the maximum extent while ensuring the desalination effect on the reverse osmosis concentrated water; wherein, when the phosphorus in the reverse osmosis concentrated water is to be recovered, high value-added vivianite can be formed.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is a schematic structural diagram of a reverse osmosis concentrated water regeneration treatment device provided by the present application;
fig. 2 is a schematic structural diagram of a reaction cell provided in the present application.
Icon: 100-reverse osmosis concentrated water regeneration treatment equipment; 110-a reaction tank; 120-a membrane module; 130-an anode plate; 140-a cathode plate; a 150-phosphorus dip tube group; 160-alkali liquor tube group; 111-electrode liquid circulation injection port; 112-a reverse osmosis concentrated water inlet; 113-a regenerated water outlet; 151-phosphorus drawing solution circulating pipe; 152-a phosphorus circulation pump; 153-a three-phase separation tank; 154-an air storage tank; 155-a three-phase separator; 156-a cone; 161-alkali liquor circulating pipe; 162-lye tank; 163-lye circulation pumps; 121-iron mesh coupled bipolar membrane; 122-cathode film; 123-anodic film; 124-bipolar membrane.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. The components of the embodiments of the present application, as generally described and illustrated in the figures herein, could be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present application, as presented in the figures, is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined or explained in subsequent figures.
In the description of the embodiments of the present application, it should be noted that the indication of orientation or positional relationship is based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship which is usually placed when the product of the application is used, or the orientation or positional relationship which is usually understood by those skilled in the art, or the orientation or positional relationship which is usually placed when the product of the application is used, and is only for the convenience of describing the application and simplifying the description, but does not indicate or imply that the indicated device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the application. Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
In the description of the embodiments of the present application, it should also be noted that, unless otherwise explicitly stated or limited, the terms "disposed," "mounted," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; may be directly connected or indirectly connected through an intermediate. The specific meaning of the above terms in the present application can be understood in a specific case by those of ordinary skill in the art.
Phosphorus (P) plays an important role in life activities, but phosphorus resources are being contaminated and phosphorus is a limited and non-renewable resource, and thus, recovery of phosphorus is of vital importance; while recovery of phosphorus from municipal reverse osmosis concentrated water plants contributes to the continuous regeneration and ecological balance of phosphorus resources, the currently widely used method for recovery of phosphorus from municipal reverse osmosis concentrated water is a crystallization method, which forms insoluble phosphate by adding an additional reagent, and the internationally common crystallization method is struvite, but the product value is low; moreover, the method is mostly suitable for the traditional enhanced biological phosphorus removal process (EBPR), and phosphorus needs to be recovered after the phosphorus-rich sludge is extracted, so the recovery efficiency is not ideal (10-50%); researchers found cyanite sludge in reverse osmosis concentrated water treatment plant sludge and accounted for most of the Fe-P conjugates; and because of the pyrite (Fe) 3 (PO 4 ) 2 ·8H 2 O) stable and easily obtained (Ksp = 10) -36 ) And economic value, and thus has received extensive attention from researchers in phosphorus recovery.
Referring to fig. 1 and 2, based on the above, the present invention provides a reverse osmosis concentrated water regeneration treatment apparatus 100, which can recover resources and energy from reverse osmosis concentrated water, and can form high value-added vivianite when phosphorus in the reverse osmosis concentrated water is to be recovered. Specifically, the reverse osmosis concentrated water regeneration treatment equipment 100 comprises a reaction tank 110, a membrane assembly 120, an anode plate 130, a cathode plate 140, a phosphorus dip tube assembly 150 and an alkali liquor tube assembly 160;
the membrane module 120, the anode plate 130 and the cathode plate 140 are all disposed in the reaction tank 110, and the membrane module 120 divides the reaction tank 110 into a phosphorus concentration chamber (marked as a in fig. 2), a desalting chamber (marked as B in fig. 2) and an alkali chamber (marked as C in fig. 2), and the phosphorus concentration chamber, the desalting chamber and the alkali chamber are all located between the anode plate 130 and the cathode plate 140; the reaction tank 110 is provided with an electrode liquid circulation injection port 111, a reverse osmosis concentrated water inlet 112 and a regenerated water outlet 113, and the electrode liquid circulation injection port 111 is used for introducing electrode liquid into the reaction tank 110; the reverse osmosis concentrated water enters the desalting chamber from a reverse osmosis concentrated water inlet 112 and is led out from a regenerated water outlet 113;
the phosphorus drawing tube group 150 and the alkali liquor tube group 160 are both communicated with the reaction tank 110; the phosphorus dip tube group 150 is used for leading out a phosphorus dip solution in the phosphorus concentration chamber and guiding the phosphorus dip solution into the phosphorus concentration chamber after separating vivianite in the phosphorus dip solution; the alkali liquor pipe group 160 is used for introducing alkali liquor into the alkali chamber.
The operating principle of the reverse osmosis concentrated water regeneration treatment equipment 100 is as follows:
the reverse osmosis concentrated water regeneration treatment equipment 100 comprises a reaction tank 110, a membrane component 120, an anode plate 130, a cathode plate 140, a phosphorus dip tube group 150 and an alkali liquor tube group 160;
the membrane module 120 divides the reaction tank 110 into a phosphorus concentration chamber, a desalting chamber and an alkali chamber, and the phosphorus concentration chamber, the desalting chamber and the alkali chamber are all positioned between the anode plate 130 and the cathode plate 140;
the reaction tank 110 is provided with an electrode liquid circulation injection port 111, a reverse osmosis concentrated water inlet 112 and a regenerated water outlet 113, and the electrode liquid circulation injection port 111 is used for introducing electrode liquid into the reaction tank 110; the reverse osmosis concentrated water enters the desalting chamber from a reverse osmosis concentrated water inlet 112 and is led out from a regenerated water outlet 113; the phosphorus drawing tube group 150 and the alkali liquor tube group 160 are both communicated with the reaction tank 110;
when the device works, reverse osmosis concentrated water enters the desalting chamber from a reverse osmosis concentrated water inlet 112, under the action of an external voltage, cations in the desalting chamber enter the alkali chamber, phosphate ions in the desalting chamber enter the phosphorus concentration chamber, and regenerated water formed after desalting of the reverse osmosis concentrated water in the desalting chamber is discharged through a regenerated water outlet 113;
the phosphorus concentration chamber is a low-concentration phosphate solution, the hydrogen ions in the phosphorus concentration chamber react with the iron net to generate ferrous ions and hydrogen, and the iron ions and the transferred phosphate ions generate a vivianite crystal;
the phosphorus draw solution flowing out of the phosphorus concentration chamber comprises the vivianite crystals, hydrogen and phosphoric acid, the separated hydrogen is stored after separation, the separated vivianite crystals are gradually separated out to generate vivianite, and the separated phosphorus draw solution circulates into the phosphorus concentration chamber again.
Therefore, the reverse osmosis concentrated water regeneration treatment equipment 100 can carry out regeneration treatment on reverse osmosis concentrated water, and can carry out resource and energy recovery to the maximum extent while ensuring the desalination effect on the reverse osmosis concentrated water; wherein, when the phosphorus in the reverse osmosis concentrated water is recovered, high value-added vivianite can be formed, and simultaneously, hydrogen can be formed.
Further, in the present embodiment, when the phosphorus dip tube group 150 is provided, in order to enable the phosphorus dip tube group 150 to function as a phosphorus dip circulation pipe, separate phosphorus dip, and store separated hydrogen gas, the phosphorus dip tube group 150 includes a phosphorus dip circulation pipe 151, a phosphorus circulation pump 152, a three-phase separation tank 153, and a gas storage tank 154;
both ends of the phosphorus draw solution circulation pipe 151 are communicated with the phosphorus concentration chamber, and the phosphorus circulation pump 152 and the three-phase separation tank 153 are communicated with the phosphorus draw solution circulation pipe 151; the phosphorus draw solution circulation pipe 151 is used for guiding the phosphorus draw solution in the phosphorus concentration chamber into the three-phase separation tank 153 under the action of the phosphorus circulation pump 152; the three-phase separation tank 153 is used for separating hydrogen and iron pyrite crystals in the phosphorus draw solution, and the separated phosphorus draw solution is introduced into the phosphorus concentration chamber through a phosphorus draw solution circulation pipe 151; the gas storage tank 154 is communicated with the three-phase separation tank 153, and serves to store the separated hydrogen gas.
Therefore, under the action of the phosphorus circulating pump 152, the phosphorus draw solution can circulate between the phosphorus concentration chamber and the phosphorus draw solution circulating pipe 151, and because the phosphorus draw solution circulating pipe 151 is communicated with the three-phase separation tank 153, hydrogen and vivianite crystals in the phosphorus draw solution can be separated under the action of the three-phase separation tank 153, and the gas storage tank 154 is communicated with the three-phase separation tank 153, so that the gas storage tank 154 can store the separated hydrogen; at this time, the separated vivianite crystals are gradually precipitated in the three-phase separation tank 153 to produce vivianite.
In order to enable the three-phase separation tank 153 to separate the phosphorus draw solution and to gradually separate the wustite crystals in the three-phase separation tank 153 to generate wustite, a three-phase separator 155 is built in the upper end of the three-phase separation tank 153, the three-phase separator 155 is used to separate hydrogen in the phosphorus draw solution, and a tapered portion 156 for collecting wustite is provided at the lower end of the three-phase separation tank 153.
Further, in the present embodiment, the lye pipe group 160 functions to form a circulation path for the lye, and thus, the lye pipe group 160 includes a lye circulation pipe 161, a lye tank 162 and a lye circulation pump 163; both ends of the alkali liquor circulating pipe 161 are communicated with the alkali chamber, and the alkali liquor tank 162 and the alkali liquor circulating pump 163 are communicated with the alkali liquor circulating pipe 161; the alkali liquor circulation pipe 161 is used for guiding the alkali liquor in the alkali liquor tank 162 into the alkali chamber under the action of the alkali liquor circulation pump 163. With this arrangement, when the concentration of the alkali solution in the alkali chamber increases, the concentration of the alkali solution in the alkali solution tank 162 can be adjusted by introducing the alkali solution into the alkali chamber.
Further, in the present embodiment, when the membrane module 120 is disposed, it includes an iron mesh coupling bipolar membrane 121, a cathode membrane 122, an anode membrane 123 and a bipolar membrane 124, the cathode membrane 122, the anode membrane 123 and the bipolar membrane 124 are sequentially arranged at intervals from the anode plate 130 to the cathode plate 140, the phosphorus concentration chamber is located between the iron mesh coupling bipolar membrane 121 and the cathode membrane 122, the desalination chamber is located between the cathode membrane 122 and the anode membrane 123, and the alkali chamber is located between the anode membrane 123 and the bipolar membrane 124 or between the anode membrane 123 and the iron mesh coupling bipolar membrane 121.
By the arrangement mode, in the working process of the reverse osmosis concentrated water regeneration treatment equipment 100, cations in the desalting chamber can permeate the anode membrane 123 to enter the alkali chamber, and phosphate ions in the desalting chamber can permeate the cathode membrane 122 to enter the phosphorus concentration chamber; and since the concentration of sodium hydroxide in the alkaline chamber is low, the concentration of alkaline solution in the alkaline chamber increases with the increase of hydroxide ions generated by the migrating cations and the anion exchange layer in the bipolar membrane 124;
in addition, since the phosphorus concentration chamber is a low-concentration phosphate solution, part of hydrogen ions generated from the cation exchange layer in the bipolar membrane 124 reacts with the iron network to generate ferrous ions and hydrogen gas, and iron ions and transferred phosphate ions can generate vivianite crystals.
In disposing the iron mesh-coupled bipolar membrane 121, in one embodiment of the present invention, the surface of the cation exchange layer of the iron mesh-coupled bipolar membrane 121 carries a layer of iron mesh of a rhombus structure having a thickness of 0.125mm to 0.25mm.
Based on the above, the present invention further provides a reverse osmosis concentrated water regeneration treatment method, which is implemented by the above reverse osmosis concentrated water regeneration treatment apparatus 100, and includes:
the reverse osmosis concentrated water is led into a desalting chamber in the reaction tank 110 through a reverse osmosis concentrated water inlet 112, under the action of an external voltage, cations enter an alkali chamber through an anode membrane 123, phosphate ions enter a phosphorus concentration chamber through a cathode membrane 122, and desalted regenerated water is discharged through a regenerated water outlet 113;
the concentration of alkali liquor in the alkali chamber is increased along with the increase of hydroxide ions generated by the migrated cations and the anion exchange layer in the bipolar membrane 124;
a low-concentration phosphate solution is arranged in the phosphorus concentration chamber, hydrogen ions generated by a cation exchange layer in the bipolar membrane 124 partially react with an iron net to generate ferrous ions and hydrogen, and the iron ions and the transferred phosphate ions generate a vivianite crystal;
the phosphorus draw solution flowing out of the phosphorus concentration chamber comprises the vivianite crystals, hydrogen and phosphoric acid, the separated hydrogen is guided into the gas storage tank 154 for storage through separation of the three-phase separation tank 153, the separated vivianite crystals are gradually separated out at the bottom end of the three-phase separation tank 153 to generate vivianite, and the separated phosphorus draw solution circulates into the phosphorus concentration chamber again.
Further, in the process of adopting the reverse osmosis concentrated water regeneration treatment method, the applied voltage of the reaction tank 110 is 1.1-1.5V; the flow rates of the reverse osmosis concentrated water, the alkali liquor and the phosphorus draw solution are all 35-50L/h; the alkali liquor is sodium hydroxide solution with the concentration of 0.02-0.05mol/L, and the phosphorus extraction solution is phosphate solution with the concentration of 0.02-0.05mol/L.
Based on the reverse osmosis concentrated water regeneration treatment equipment 100 and the method, in the process of carrying out reverse osmosis water regeneration treatment, a layer of rhombic iron net with the thickness of 0.13mm is loaded on the surface of a cation exchange layer of an iron net coupling bipolar membrane 121, the operating voltage is controlled to be 1.25V, the flow rates of reverse osmosis concentrated water, alkali liquor and phosphorus draw solution are 40L/h, the alkali liquor adopts sodium hydroxide solution, the initial concentration is controlled to be 0.03mol/L, the phosphorus draw solution adopts phosphate solution, the initial concentration is controlled to be 0.03mol/L, and the effluent water quality and resource recovery data are shown in Table 1;
TABLE 1
A layer of diamond-structured iron net with the thickness of 0.15mm is loaded on the surface of the cation exchange layer of the iron net coupling bipolar membrane 121, the operating voltage is controlled to be 1.4V, the flow rates of reverse osmosis concentrated water, alkali liquor and phosphorus drawing liquid are 37L/h, the alkali liquor adopts sodium hydroxide solution and the initial concentration is controlled to be 0.04mol/L, the phosphorus drawing liquid adopts phosphate solution and the initial concentration is controlled to be 0.04mol/L, and the effluent quality and resource recovery data are shown in Table 2.
TABLE 2
A layer of diamond-structured iron net with the thickness of 0.13mm is loaded on the surface of the cation exchange layer of the iron net coupling bipolar membrane 121, the operating voltage is controlled to be 1.1V, the flow rates of reverse osmosis concentrated water, alkali liquor and phosphorus drawing liquid are 47L/h, the alkali liquor adopts sodium hydroxide solution and the initial concentration is controlled to be 0.05mol/L, the phosphorus drawing liquid adopts phosphate solution and the initial concentration is controlled to be 0.05mol/L, and the effluent quality and resource recovery data are shown in Table 3.
TABLE 3
In conclusion, the reverse osmosis concentrated water regeneration treatment equipment 100 and the method have the following beneficial effects that the bipolar membrane 124 mode can be utilized to ensure the desalination effect of reverse osmosis concentrated water and carry out resource and energy recovery to the maximum extent in the process of carrying out the regeneration treatment of reverse osmosis concentrated water; recovering phosphorus in the concentrated water through the concentration effect of electrodialysis on ions to form high-added-value vivianite; zero-valent iron is used as a reducing agent to reduce hydrogen ions into hydrogen, and the hydrogen is recycled as energy.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A reverse osmosis concentrated water regeneration treatment equipment is characterized in that:
the reverse osmosis concentrated water regeneration treatment equipment comprises a reaction tank, a membrane component, an anode plate, a cathode plate, a phosphorus dip tube group and an alkali liquor tube group;
the membrane assembly, the anode plate and the cathode plate are all arranged in a reaction tank, the reaction tank is divided into a phosphorus concentration chamber, a desalting chamber and an alkali chamber by the membrane assembly, and the phosphorus concentration chamber, the desalting chamber and the alkali chamber are all positioned between the anode plate and the cathode plate; the reaction tank is provided with an electrode liquid circulating injection hole, a reverse osmosis concentrated water inlet and a regenerated water outlet, and the electrode liquid circulating injection hole is used for introducing electrode liquid into the reaction tank; reverse osmosis concentrated water enters the desalting chamber from the reverse osmosis concentrated water inlet and is led out from the regenerated water outlet;
the phosphorus drawing pipe group and the alkali liquor pipe group are both communicated with the reaction tank; the phosphorus draw tube group is used for leading out a phosphorus draw solution in the phosphorus concentration chamber and leading the phosphorus draw solution into the phosphorus concentration chamber after separating the vivianite in the phosphorus draw solution; the alkali liquor pipe group is used for introducing alkali liquor into the alkali chamber.
2. A reverse osmosis concentrated water regeneration treatment apparatus according to claim 1, characterized in that:
the phosphorus drawing pipe group comprises a phosphorus drawing liquid circulating pipe, a phosphorus circulating pump, a three-phase separation tank and a gas storage tank;
both ends of the phosphorus drawing liquid circulating pipe are communicated with the phosphorus concentration chamber, and the phosphorus circulating pump and the three-phase separation tank are communicated with the phosphorus drawing liquid circulating pipe; the phosphorus drawing liquid circulating pipe is used for guiding the phosphorus drawing liquid in the phosphorus concentration chamber into the three-phase separation tank under the action of the phosphorus circulating pump; the three-phase separation tank is used for separating hydrogen and vivianite crystals from the phosphorus draw solution, and the separated phosphorus draw solution is led into the phosphorus concentration chamber through the phosphorus draw solution circulating pipe;
and the gas storage tank is communicated with the three-phase separation tank and is used for storing the separated hydrogen.
3. A reverse osmosis concentrated water regeneration treatment apparatus according to claim 2, characterized in that:
the upper end of the three-phase separation tank is internally provided with a three-phase separator, the three-phase separator is used for separating hydrogen in the phosphorus extraction liquid, and the lower end of the three-phase separation tank is provided with a conical part used for collecting the vivianite.
4. A reverse osmosis concentrated water regeneration treatment apparatus according to claim 1, characterized in that:
the alkali liquor pipe group comprises an alkali liquor circulating pipe, an alkali liquor tank and an alkali liquor circulating pump;
both ends of the alkali liquor circulating pipe are communicated with the alkali chamber, and the alkali liquor tank and the alkali liquor circulating pump are communicated with the alkali liquor circulating pipe;
the alkali liquor circulating pipe is used for guiding the alkali liquor in the alkali liquor tank into the alkali chamber under the action of the alkali liquor circulating pump.
5. A reverse osmosis concentrated water regeneration treatment apparatus according to any one of claims 1 to 4, wherein:
the membrane module includes indisputable net coupling bipolar membrane, negative pole membrane, anode film and bipolar membrane, bipolar membrane the negative pole membrane the anode film and bipolar membrane by the anode plate extremely the direction of negative plate is interval arrangement in proper order, just the concentrated room of phosphorus is located indisputable net coupling bipolar membrane with between the negative pole membrane, the desalination room is located the cathode film with between the anode film, the alkali chamber is located anode film with between the bipolar membrane or be located the anode film with between the indisputable net coupling bipolar membrane.
6. A reverse osmosis concentrated water regeneration treatment apparatus according to claim 5, characterized in that:
the surface of the cation exchange layer of the iron net coupling bipolar membrane is loaded with a layer of diamond-structured iron net, and the thickness of the iron net is 0.125mm-0.25mm.
7. A reverse osmosis concentrated water regeneration treatment method implemented by the reverse osmosis concentrated water regeneration treatment apparatus according to any one of claims 1 to 6, comprising:
leading reverse osmosis concentrated water into the desalting chamber in the reaction tank through the reverse osmosis concentrated water inlet, allowing cations to enter the alkali chamber through an anode membrane under the action of an external voltage, allowing phosphate ions to enter the phosphorus concentration chamber through a cathode membrane, and discharging desalted regenerated water through the regenerated water outlet;
the alkali chamber is low-concentration sodium hydroxide, and the concentration of alkali liquor in the alkali chamber is increased along with the increase of hydroxide ions generated by the migrated cations and an anion exchange layer in the bipolar membrane;
a low-concentration phosphate solution is arranged in the phosphorus concentration chamber, part of hydrogen ions generated by a cation exchange layer in the bipolar membrane react with an iron net to generate ferrous ions and hydrogen, and the iron ions and the transferred phosphate ions generate vivianite crystals;
the phosphorus drawing liquid flowing out of the phosphorus concentration chamber comprises a vivianite crystal, hydrogen and phosphoric acid, the separated hydrogen is guided into the gas storage tank for storage through separation of the three-phase separation tank, the separated vivianite crystal is gradually separated out at the bottom end of the three-phase separation tank to generate vivianite, and the separated phosphorus drawing liquid circulates into the phosphorus concentration chamber again.
8. A reverse osmosis concentrated water regeneration treatment method according to claim 7, characterized in that:
the applied voltage of the reaction tank is 1.1-1.5V.
9. A reverse osmosis concentrated water regeneration treatment method according to claim 7, characterized in that:
the flow rates of the reverse osmosis concentrated water, the alkali liquor and the phosphorus extraction liquid are all 35-50L/h.
10. A reverse osmosis concentrated water regeneration treatment method according to claim 7, characterized in that:
the alkali liquor is sodium hydroxide solution, and the concentration of the alkali liquor is 0.02-0.05mol/L;
the phosphorus extraction solution is phosphate solution, and the concentration of the phosphate solution is 0.02-0.05mol/L.
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| JP2001070989A (en) * | 1999-09-07 | 2001-03-21 | Ebara Corp | Method and apparatus for treating organic wastewater containing high concentration of salts |
| CN106630040A (en) * | 2016-12-28 | 2017-05-10 | 中国科学技术大学 | Selective bipolar membrane electrodialysis system and application thereof |
| CN107555555A (en) * | 2017-10-07 | 2018-01-09 | 山东科技大学 | One kind is based on the positive infiltration technology high salt process for treating high-COD waste water of electrodialysis and its device |
| CN110902781A (en) * | 2019-12-14 | 2020-03-24 | 西安建筑科技大学 | Device and method for treating phosphorus-containing wastewater and recycling phosphorus resources by iron-air battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001070989A (en) * | 1999-09-07 | 2001-03-21 | Ebara Corp | Method and apparatus for treating organic wastewater containing high concentration of salts |
| CN106630040A (en) * | 2016-12-28 | 2017-05-10 | 中国科学技术大学 | Selective bipolar membrane electrodialysis system and application thereof |
| CN107555555A (en) * | 2017-10-07 | 2018-01-09 | 山东科技大学 | One kind is based on the positive infiltration technology high salt process for treating high-COD waste water of electrodialysis and its device |
| CN110902781A (en) * | 2019-12-14 | 2020-03-24 | 西安建筑科技大学 | Device and method for treating phosphorus-containing wastewater and recycling phosphorus resources by iron-air battery |
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