CN105836936A - An ammonia nitrogen recovering method based on membrane electroadsorption and ion exchange - Google Patents
An ammonia nitrogen recovering method based on membrane electroadsorption and ion exchange Download PDFInfo
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- CN105836936A CN105836936A CN201610220895.9A CN201610220895A CN105836936A CN 105836936 A CN105836936 A CN 105836936A CN 201610220895 A CN201610220895 A CN 201610220895A CN 105836936 A CN105836936 A CN 105836936A
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000005342 ion exchange Methods 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000012528 membrane Substances 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000010865 sewage Substances 0.000 claims abstract description 27
- 238000011084 recovery Methods 0.000 claims abstract description 26
- 239000011575 calcium Substances 0.000 claims abstract description 25
- 239000011777 magnesium Substances 0.000 claims abstract description 23
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001768 cations Chemical class 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims description 33
- 150000002500 ions Chemical class 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 23
- 238000010521 absorption reaction Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 238000010612 desalination reaction Methods 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229910001424 calcium ion Inorganic materials 0.000 claims description 5
- 238000005341 cation exchange Methods 0.000 claims description 4
- 239000010842 industrial wastewater Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003456 ion exchange resin Substances 0.000 abstract description 8
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 230000008929 regeneration Effects 0.000 abstract description 7
- 238000011069 regeneration method Methods 0.000 abstract description 7
- 238000011033 desalting Methods 0.000 abstract description 4
- 239000010802 sludge Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 2
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- 239000003014 ion exchange membrane Substances 0.000 description 7
- 239000013505 freshwater Substances 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- -1 salt ion Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003010 cation ion exchange membrane Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002592 echocardiography Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000007483 microbial process Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
-
- 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
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
An ammonia nitrogen recovering method based on membrane electroadsorption and ion exchange is provided. The method includes three steps, namely steps of performing membrane electroadsorption desalting pretreatment to remove calcium, magnesium and other divalent cations from waste water, adsorbing ammonia nitrogen through ion exchange, and regenerating and recovering the ammonia nitrogen through desorbing an ion exchange column, and the like. For critical town sewage, the hardness of water is about 400 mg/L (counted based on calcium carbonate), and selectivity of the calcium, the magnesium and other cations in ion exchange resin is superior to that of the ammonia nitrogen, and therefore existence of the calcium, the magnesium and other cations leads to a situation that a pure ion exchange process cannot achieve effective recovery of the ammonia nitrogen. The method effectively overcomes the problem of recovering the ammonia nitrogen in low-ammonia-nitrogen waste water with the existence of the cations by utilizing the membrane electroadsorption desalting pretreatment, allows the waste water to be discharged after reaching the standards at the same time of ammonia nitrogen recovery, greatly reduces the regeneration frequency of the ion exchange resin, and increases the ammonia nitrogen adsorbing recovering capability of the ion exchange column by one time or above. In addition, the method is low in energy consumption, small in occupied space, free of generation of sludge and free of generation of harmful substances, and greatly reduces the treating cost.
Description
Technical field
The present invention relates to resource circulation utilization technical field, be specifically related to a kind of ammonia nitrogen recovery method exchanged based on film electro-adsorption and ion.
Background technology
In recent years, the raising required quality of water environment along with people, sewage drainage standard is the strictest.Conventional water treatment system is difficult to efficiently remove the ammonia nitrogen in water, especially when ammonia nitrogen concentration is the highest but the most up to standard time, activated sludge is that the biological treatment system of representative needs to increase backflow, increase the measures such as Chi Rong, water outlet can be only achieved discharge standard, and increase backflow and need a large amount of energy consumptions, increasing pond and hold a large amount of inputs needing soil, consumptive material, these measures often seem less economical.
On the other hand, in the today pursuing sustainable development, people start exploration and recycle water, resource and the energy from sewage treatment plant as far as possible.The conventional treatment microbial process based on nitrification-denitrification of nitrogen element in sewage at present.If the ammonia nitrogen in sewage is considered as a kind of new nitrogen source, then this conventional process only achieves the Environmental capacity of nitrogen element, the recovery of unrealized nitrogen.
It is true that nitrogen element circular is the important component part of nature material circulation, the nitrogen of nature is changed into ammonia nitrogen by ammonia synthesis reaction and is used by the mankind, and this needs to consume substantial amounts of energy.If nitrogen in sewage can be made full use of, the high energy consumption during tradition on the one hand can be avoided to remove ammonia nitrogen, save the energy consumption producing respective amount ammonia nitrogen while on the other hand can reclaiming nitrogen.But, lack at present and can realize the technical matters that ammonia nitrogen in sewage is effectively removed and reclaimed simultaneously.
Electro-adsorption desalting technology utilizes electric field force to realize removal (the i.e. capacitive deionization technology Capacitive deionization of salt ion, CDI), it is at lower voltages (about 1.2V), the zwitterion displacement in solution is made to form electric double layer on porous adsorption electrode, it is achieved to the removal of zwitterion in solution.If respectively plus cation and anion exchange membrane, i.e. " film electro-adsorption technology (Membrane between anode and cathode and solution
Capacitive deionization, MCDI) ", capacity and the ion selectivity of electro-adsorption can be improved.The operation voltage of electro-adsorption desalting technology is only 1.2V, and electric field force directly acts on the ion in water, and electric charge efficiency is up to more than 60% (MCDI electric charge efficiency can reach more than 90%), which dictates that the green energy conservation characteristic of CDI.Experiment proves that, film electro-adsorption has more preferable selectivity to divalent ions such as calcium and magnesium, and order is Ca2+>Mg2+>K+>NH4 +>Na+；If ion exchange membrane is modified, more preferable ion selectivity can be made it have.
The attached ammonia nitrogen of ion-exchange absorption is the method removing ammonia nitrogen that comparison is traditional.Compared with traditional wastewater, it is relatively low that ion exchange need not aeration, backflow energy consumption, and the time of staying is little, facility compact is taken up an area little, removes ammonia nitrogen process and does not produce activated sludge, and resin regeneration simultaneously can be enriched with ammonia nitrogen and be beneficial to reclaim.Ion exchange process includes two processes: 1) sodium ion on Na type (or H type) cationic resin is cemented out (selectivity: Ca by absorption ammonium radical ion2+>Mg2+>NH4 +>Na+)；2) sodium (hydrogen) ion of regeneration high concentration is ammonia nitrogen eluting.The adsorption process that so can utilize ion exchange column removes ammonia nitrogen in sewage, and regenerative process obtains the ammonia nitrogen regenerated liquid of high concentration while recovering resin absorption ability, is conducive to reclaiming ammonia nitrogen further.
But for typical town sewage, ammonia nitrogen concentration is about 40mg/L, and the hardness in water is about 400, and the selectivity that calcium and magnesium plasma is on ion exchange resin is better than ammonia nitrogen, owing in the sewage of Typical Towns, calcium ions and magnesium ions exists in a large number so that simple ion exchange process is difficult to the efficient recovery of ammonia nitrogen.Then the present invention proposes to utilize the ion selectivity removal process attached to ion-exchange absorption of MCDI to carry out pretreatment, thus proposes a kind of ammonia nitrogen recovery method exchanged based on film electro-adsorption and ion.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of ammonia nitrogen recovery method exchanged based on film electro-adsorption and ion, solution traditional biological processes ammonia nitrogen energy consumption height, efficiency is low, cannot fully recycle the problems such as ammonia nitrogen.The present invention is applicable to the situations such as sanitary sewage, Sewage Plant secondary effluent, low ammonia nitrogen industrial wastewater.
For achieving the above object, the present invention provides technical scheme as follows:
A kind of ammonia nitrogen recovery method exchanged based on film electro-adsorption and ion, comprises the following steps:
Step one, film electro-adsorption desalination pretreatment: this process utilizes film electro-adsorption (MCDI) technology can the bivalent cation such as calcium, magnesium in selective removal waste water；
Step 2, the attached ammonia nitrogen of ion-exchange absorption: reclaim in ammonia nitrogen system in ion exchange, utilize ion exchange to adsorb ammonia nitrogen, ammonia nitrogen is enriched in ion exchange column；
Step 3, ion exchange reclaims ammonia nitrogen: with the ammonia nitrogen of enrichment in the salt of high concentration or acid solution desorption procedure two thus the ammonia nitrogen solution being recycled；
Wherein, porous carbon materials is commercial activated carbon, dense water is sanitary sewage, Sewage Plant secondary effluent or low ammonia nitrogen industrial wastewater, and stripping liquid is NaCl solution or the HCl solution of 20%, and ion exchange column is the strong acid cation resin of strongly acidic cation-exchange post or other models.
After MCDI desalination pretreatment, in waste water, calcium and magnesium sum is reduced to 1: 1 with the mol ratio of ammonia nitrogen by 4: 1.5, electric charge mol ratio is reduced to 2: 1(by 5: 1 and is reduced in terms of 2mmol/L: 1mmol/L by 5mmol/L:1mmol/L), before and after pretreatment, treatment on ion exchange columns sewage ability can improve more than 1 times.
4 cycles connect electro-adsorption-short circuit desorbing after, Mg2+And Ca2+Clearance be up to 74.5% and 71.3%, Na+、NH4 +And K+Clearance be respectively 7.2%, 20.0% and 25.0%.
The ammonia nitrogen recovery method of the present invention has the characteristics that and beneficial effect:
(1) compared with traditional wastewater, energy consumption is relatively low, it is little to take up an area, and does not produce mud, can reclaim ammonia nitrogen simultaneously；
(2) compared with the chemical methodes such as breakpoint chlorination, harmful substance etc. is not produced；
(3) compared with traditional ion exchange, eliminate the isoionic interference of calcium and magnesium, ignore sodium ion and ion exchange column the selectivity of different ions is affected, in the ammonia nitrogen recovery method of the embodiment of the present invention, ion exchange column absorption is reclaimed the ability of ammonia nitrogen and is more than doubled, greatly reduce regeneration of ion-exchange resin frequency, thus advantageously reduce cost.
Accompanying drawing explanation
The invention will be further described below in conjunction with the accompanying drawings:
Fig. 1 is film electro-adsorption (MCDI) schematic diagram of the embodiment of the present invention；
Fig. 2 is the ion exchange flow chart of the embodiment of the present invention；
Fig. 3 is the ammonia nitrogen recovery system flow chart of the embodiment of the present invention；
Fig. 4 is that the MCDI of the embodiment of the present invention is to calcium, the comparison diagram of magnesium ion selective removal..
In Fig. 1,1 is porous carbon materials, and 2 is ion exchange membrane, and 3a is positive pole, and 3c is negative pole, 4 for dense water, and 5 is fresh water.
In Fig. 2,6 is water inlet, and 7 is water outlet, and 8 is stripping liquid, and 9 is dense ammonia nitrogen solution, and 10 is ion exchange column, and 11 is peristaltic pump.
In Fig. 3, A is MCDI pretreatment system, and B is that ion exchanges (IX) recovery system；12 is water inlet, and 13 is MCDI module, and 14 is thin liquid I, and 15 is dope I, and 10 is ion exchange column, and 16 is thin liquid II (water outlet), and 17 is dope II (dense ammonia nitrogen liquid)；A is for connecing electro-adsorption, and b is short circuit desorbing, and c is for repeatedly to circulate, and d is absorption, and e is that ammonia nitrogen reclaims.
Detailed description of the invention
Below in conjunction with accompanying drawing, the embodiment of the present invention is described in detail.
During ion exchange resin reclaims ammonia nitrogen, due to calcium, magnesium, potassium, the isoionic impact of sodium, the especially impact of the bivalent cation such as calcium, magnesium in water so that resin is undesirable to the recovering effect of ammonia nitrogen.And migration velocity that the nature differences such as the valence state of ion and radius can cause ion is different, the present invention utilizes film electro-adsorption (MCDI) technology difference to the clearance of different ions, and MCDI recycles the pretreatment section of ammonia nitrogen technique as ion exchange resin.By the selective absorption of MCDI, the most first remove the bivalent cation such as deliming, magnesium, improve ion exchange resin and recycle the effect of ammonia nitrogen, can effectively reduce the regeneration frequency of resin, be substantially reduced cost.
The present embodiment provides a kind of ammonia nitrogen recovery method exchanged based on film electro-adsorption and ion, reclaims three steps such as ammonia nitrogen including the exchange of film electro-adsorption desalination processes pretreatment (MCDI), the attached ammonia nitrogen of ion-exchange absorption and ion, is embodied as step as follows:
Step one: film electro-adsorption desalination processes pretreatment (MCDI)
The purpose of pretreatment is to remove the bivalent cation such as calcium, magnesium ion in sewage.Fig. 1 show film electro-adsorption (MCDI) schematic diagram of the embodiment of the present invention.Including porous carbon materials 1 in Fig. 1, ion exchange membrane 2, positive pole 3a, negative pole 3c, dense water 4, fresh water 5.The denseest water 4 can be the sewage such as sanitary sewage, Sewage Plant secondary effluent or low ammonia nitrogen industrial wastewater.The isoionic dense water 4 of calcic, magnesium and ammonia nitrogen circulates through MCDI with certain flow rate, and voltage stabilization is at 1.0-1.3V.Under voltage produces the effect of electric field force, in sewage 4, anions and canons migrates to positive pole 3a and negative pole 3c respectively and forms electric double layer on porous carbon materials 1, above-mentioned porous carbon materials 1 can select commercial activated carbon, the most corresponding anion exchange membrane of positive and negative electrode and cation exchange membrane.Ion exchange membrane 2 can eliminate the impact on electric double layer of the water intermediate ion through cation or anion simultaneously；In transition process, bivalent cation (Ca2+、Mg2+) migration velocity be faster than monovalent cation (Na+、K+、NH4 +).Along with ion is to the migration of electrode, dirty electrical conductivity of water can decline, when electrical conductivity no longer declines, and electric current vanishing, now think that absorption is saturated, obtain the fresh water 5 processed；Short circuit electrode 3a and 3c, flows through MCDI with the most untreated sewage 4, and the electric double layer on electrode disappears, and ion adsorbed on ion exchange membrane obtains desorbing, and dirty electrical conductivity of water rises, when electrical conductivity no longer rises, when electric current is zero, it is believed that desorbing is complete.Repeat above-mentioned process, until dense water 4 electrical conductivity drops to the content of calcium and magnesium reduction certain value (being to reduce to about 800us/cm from 1400 in this example) now water substantially (reducing to 29mg/L and 9mg/L from 100mg/L and 33mg/L respectively in the present embodiment) in MCDI, ammonia nitrogen is the most a small amount of to be reduced, this shows that the bivalent cations such as the calcium in sewage 4, magnesium can be significantly removed in MCDI pretreatment, simultaneously the least on the concentration impact of ammonia nitrogen in sewage 4, thus take a firm foundation for following steps reclaim ammonia nitrogen.
In step one, the cycle-index of MCDI pretreatment system MCDI, electrode area size, the modification of ion exchange membrane, series connection number and operator scheme (intermittently or serially) can be changed accordingly according to water inlet character, pre-processing requirements.
Step 2: the attached ammonia nitrogen of ion-exchange absorption.
It is illustrated in figure 2 the ion exchange flow chart of the embodiment of the present invention.In Fig. 2,6 is water inlet, and 7 is water outlet, and 8 is stripping liquid, and 9 is dense ammonia nitrogen solution, and 10 is ion exchange column, and 11 is peristaltic pump.Above-mentioned ion exchange column 10 can be strongly acidic cation-exchange post, it is also possible to select the cationic resin of different model based on adsorption capacity, requires to select single, mixed bed isotype based on water outlet PH.In Fig. 2, the ion exchange column 10 that is shown in solid adsorbs the process of ammonia nitrogen.Dense water 4 is after MCDI pretreatment in step one, in fresh water 5, the divalent ion content such as calcium and magnesium is decreased obviously, clearance all reaches more than 71%, now in Fig. 1, fresh water 5 is in Fig. 2 water inlet 6, and water inlet 6 passes through the effect of peristaltic pump 11 with certain flow rate through ion exchange column 10, through base exchange process, ammonia nitrogen in waste water 6 is adsorbed, i.e. can obtain eliminating the water outlet 7 of ammonia nitrogen, in the process, ammonia nitrogen absorption is constantly enriched with by ion exchange column 10.At the ion exchange process initial stage, in water outlet 7, ammonia-nitrogen content cannot detect substantially.In ion exchange process latter stage, when rising occurs in ammonia nitrogen concentration in water outlet 7, it is believed that ion exchange column 10 adsorbs saturated, stop adsorption process, enter next stage, ammonia nitrogen recovery stage.
Step 3: ammonia nitrogen is reclaimed in ion exchange.
Fig. 2 is shown in dotted line the process reclaiming ammonia nitrogen.Stripping liquid 8 is flowed through with relatively low flow velocity by the effect of peristaltic pump 11 and adsorbs saturated ion exchange resin column 10 in step 2, obtains dense ammonia nitrogen solution 9, it is achieved the recovery to ammonia nitrogen.Above-mentioned stripping liquid 8 can be about the NaCl concentrated solution of 20%, it is also possible to select salt or the acid solution of high concentration according to the existence form of ammonia nitrogen in follow-up ammonia nitrogen dope.Indicate ammonia nitrogen concentration with nessler reagent, in removal process, record time the water outlet of ion exchange column 10 no longer has ammonia nitrogen, complete ammonia nitrogen and reclaim.
System have devised ammonia nitrogen recovery system flow chart as shown in Figure 3, including MCDI pretreatment system A, ion exchange (IX) recovery system B, water inlet 12, MCDI module 13,14 for thin liquid I, 15 be dope I, ion exchange column 10,16 for thin liquid II, 17 for dope II (dense ammonia nitrogen liquid), a for connecing electro-adsorption, b is short circuit desorbing, c is repeatedly circulation, d is absorption, e is ammonia nitrogen recovery.Wherein, having the place that a few place is consistent in Fig. 3 with Fig. 1, Fig. 2, water inlet 12 is consistent with dense water 4,14 be thin liquid I with fresh water 5, intake 6 consistent, thin liquid II 16 is consistent with water outlet 7, and dope II 17 is consistent with dense ammonia nitrogen solution 9.It is in series it addition, the MCDI module 13 in MCDI pretreatment system A can be multiple module 13.According to the waste water of film pre-concentration reactor water outlet configuration present case, configure simulated wastewater 12 with calcium chloride, potassium chloride, magnesium chloride, sodium chloride and ammonium chloride.Wherein various ion concentration can be following composition: Ca:100mg/L, K:10 mg/L, Mg:33 mg/L, Na:72 mg/L, NH4: 20 mg/L.Take the above-mentioned water inlet of 150mL 12, circulate to electrical conductivity in MCDI pretreatment system A constant after take 5mL as treat test sample survey ammonia nitrogen concentration therein be 20mg/L.Meet unidirectional current 1.2V, until electrical conductivity no longer declines, electric current vanishing, now think that absorption is saturated, complete to meet electro-adsorption a, obtain thin liquid I 14, survey its each ion concentration；With the ion of 20mL deionized water short circuit desorbing b absorption, electrical conductivity no longer rises, and when electric current is zero, completes short circuit desorbing, obtains the dope I 15 of calcium-magnesium-containing ion.After repeatedly circulating c, complete MCDI pretreatment, record the mass concentration of each ion: Ca:29mg/L, K:5mg/L, Mg:9mg/L, Na:83 mg/L, NH4: 16 mg/L.In native system, repeat above-mentioned to meet electro-adsorption a and short circuit desorbing b 4 times, until electrical conductivity reduces to about 800, then completion system MCDI pretreatment.Cation situation in 4 all after date water: being reduced to 1: 1 from the mol ratio of water inlet 12 to thin liquid I 14, calcium and magnesium sum and ammonia nitrogen by 4: 1.5, electric charge mol ratio is reduced to 2: 1 by 5: 1, and this shows that hardness of water drops to 100(with CaCO from 3903Note), and ammonia nitrogen concentration change is little.
Fig. 4 be in the embodiment of the present invention MCDI to calcium, the Comparative result figure of magnesium ion selective removal.It can be seen that 4 cycles connect electro-adsorption short circuit desorbing after, Na+、NH4 +And K+Changes of contents less, clearance is respectively 7.2%, 20.0% and 25.0%；And the clearance of Mg and Ca is up to 74.5% and 71.3%.
Sewage, after MCDI pretreatment system A pretreatment, enters ion exchange (IX) recovery system B.Thin liquid I 14 pumps into ion exchange column 10 with certain flow rate, and the ammonia nitrogen in base exchange process, waste water 14 is adsorbed d, i.e. can obtain eliminating the thin liquid II 16 of ammonia nitrogen；In ion exchange process latter stage, when thin liquid II 16 has ammonia nitrogen concentration to occur, it is believed that ion exchange column absorption is saturated, stop adsorption process.Enter ammonia nitrogen recovery stage, pump into the saturated ion exchange resin column 10 of absorption with regenerated liquid 8 with relatively low flow velocity and carry out reclaiming e, obtain dope II 17(dense ammonia nitrogen liquid), it is achieved the recovery to ammonia nitrogen, when water outlet no longer has ammonia nitrogen, complete ammonia nitrogen removal process.
In terms of the operation mechanism of ion exchange, ignore sodium ion and ion exchange column the selectivity of different ions is affected, it is believed that in the ammonia nitrogen recovery method of the embodiment of the present invention, the capacity of ion exchange column absorption ammonia nitrogen is doubled, and regeneration frequency reduces about half.If improving the selectivity (such as ion exchange membrane being modified) of MCDI further so that in the thin liquid I 14 after MCDI, the divalent ion such as calcium, magnesium is significantly removed, then regeneration of ion-exchange resin cost will be greatly reduced on the basis of existing again.
From the perspective of ammonia nitrogen reclaims, ion-exchange absorption echos regenerative process and can be reclaimed completely by the ion in water, cationic resin (counting for 6mmol/g with adsorption capacity) for certain adsorption capacity, before and after pretreatment, calcium and magnesium sum and ammonia nitrogen electric charge mol ratio are reduced to 2: 1(by 5: 1 and are reduced in terms of 2mmol/L: 1mmol/L by 5mmol/L: 1mmol/L), then before pretreatment, 1g resin can process 1L Water Sproading 1mmol ammonia nitrogen, 2L Water Sproading 2mmol ammonia nitrogen (even if the ammonia nitrogen loss of 20%, the most recyclable 1.6mmol when counting pretreatment) can be processed after pretreatment.
It should be noted that it is less and the most just can cannot remove divalent ion completely based on adsorbing material on electrode slice that MCDI in present case circulates the operation of 4 times；Cycle-index in actual application can determine according to the amount of influent concentration and porous carbon adsorbing material, the number of times that additionally by multiple block coupled in series, increase electrode slice area and adsorbing material load capacity, can also reduce circulation operation even realizes the continuous operation of MCDI pretreatment unit.
For those skilled in the art, on the basis of above-mentioned principle, it is also possible to the method for the invention is made some changes and improvements, within these changes and improvements also should be included in protection scope of the present invention.
Claims (3)
1. the ammonia nitrogen recovery method exchanged based on film electro-adsorption and ion, wherein, comprises the following steps:
Step one, film electro-adsorption desalination pretreatment: this process utilizes film electro-adsorption (MCDI) technology can the bivalent cation such as calcium, magnesium in selective removal waste water；
Step 2, the attached ammonia nitrogen of ion-exchange absorption: reclaim in ammonia nitrogen system in ion exchange, utilize ion exchange to adsorb ammonia nitrogen, ammonia nitrogen is enriched in ion exchange column (10)；
Step 3, ion exchange reclaims ammonia nitrogen: with the ammonia nitrogen of enrichment in the salt of high concentration or acid solution desorption procedure two thus the ammonia nitrogen solution (17) being recycled；
Wherein, porous carbon materials (1) is commercial activated carbon, dense water (4) is sanitary sewage, Sewage Plant secondary effluent or low ammonia nitrogen industrial wastewater, stripping liquid (8) is NaCl solution or the HCl solution of 20%, and ion exchange column (10) is the strong acid cation resin of strongly acidic cation-exchange post or other models.
Ammonia nitrogen recovery method the most according to claim 1, it is characterized in that: after MCDI desalination pretreatment, in waste water, calcium and magnesium sum is reduced to 1: 1 with the mol ratio of ammonia nitrogen by 4: 1.5, electric charge mol ratio is reduced to 2: 1(by 5: 1 and is reduced in terms of 2mmol/L: 1mmol/L by 5mmol/L:1mmol/L), before and after pretreatment, treatment on ion exchange columns sewage ability can improve more than 1 times.
Ammonia nitrogen recovery method the most according to claim 1 or claim 2, it is characterised in that: 4 cycles connect electro-adsorption-short circuit desorbing after, Mg2+And Ca2+Clearance be up to 74.5% and 71.3%, Na+、NH4 +And K+Clearance be respectively 7.2%, 20.0% and 25.0%.
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| CN108502987A (en) * | 2018-03-16 | 2018-09-07 | 天津市海跃水处理高科技有限公司 | A kind of fast purification method of pharmacy centre waste water |
| CN114082301A (en) * | 2021-10-18 | 2022-02-25 | 江苏核电有限公司 | Separation system, method and detection method for isotope iodine in nuclear power plant coolant |
| CN117417094A (en) * | 2023-12-06 | 2024-01-19 | 中国化学工程第六建设有限公司 | A recycling treatment method and system for industrialized freshwater aquaculture water bodies |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107298513A (en) * | 2017-08-07 | 2017-10-27 | 南京林业大学 | The preparation method and its special purpose device of a kind of complex fertilizer |
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| CN114082301B (en) * | 2021-10-18 | 2024-04-09 | 江苏核电有限公司 | Separation system, method and detection method for isotope iodine in nuclear power plant coolant |
| CN117417094A (en) * | 2023-12-06 | 2024-01-19 | 中国化学工程第六建设有限公司 | A recycling treatment method and system for industrialized freshwater aquaculture water bodies |
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