CN104591336B - A kind of from containing the method reclaiming phosphorus fosfomycin waste water - Google Patents
A kind of from containing the method reclaiming phosphorus fosfomycin waste water Download PDFInfo
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- CN104591336B CN104591336B CN201510039059.6A CN201510039059A CN104591336B CN 104591336 B CN104591336 B CN 104591336B CN 201510039059 A CN201510039059 A CN 201510039059A CN 104591336 B CN104591336 B CN 104591336B
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- phosphorus
- fosfomycin
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- waste water
- product
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000011574 phosphorus Substances 0.000 title claims abstract description 123
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 123
- YMDXZJFXQJVXBF-STHAYSLISA-N fosfomycin Chemical compound C[C@@H]1O[C@@H]1P(O)(O)=O YMDXZJFXQJVXBF-STHAYSLISA-N 0.000 title claims abstract description 52
- 229960000308 fosfomycin Drugs 0.000 title claims abstract description 52
- 239000002351 wastewater Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 18
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000378 calcium silicate Substances 0.000 claims abstract description 15
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 10
- 239000010935 stainless steel Substances 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 239000011780 sodium chloride Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 36
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 abstract description 14
- 238000013019 agitation Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000002686 phosphate fertilizer Substances 0.000 abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 16
- 230000002572 peristaltic effect Effects 0.000 description 12
- 239000010452 phosphate Substances 0.000 description 11
- 239000001506 calcium phosphate Substances 0.000 description 8
- 229910000389 calcium phosphate Inorganic materials 0.000 description 8
- 235000011010 calcium phosphates Nutrition 0.000 description 8
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ZKHQWZAMYRWXGA-KQYNXXCUSA-J ATP(4-) Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O)[C@@H](O)[C@H]1O ZKHQWZAMYRWXGA-KQYNXXCUSA-J 0.000 description 2
- ZKHQWZAMYRWXGA-UHFFFAOYSA-N Adenosine triphosphate Natural products C1=NC=2C(N)=NC=NC=2N1C1OC(COP(O)(=O)OP(O)(=O)OP(O)(O)=O)C(O)C1O ZKHQWZAMYRWXGA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- QZIQJIKUVJMTDG-OTUWWBTESA-L disodium;[(2s,3r)-3-methyloxiran-2-yl]-dioxido-oxo-$l^{5}-phosphane Chemical compound [Na+].[Na+].C[C@H]1O[C@H]1P([O-])([O-])=O QZIQJIKUVJMTDG-OTUWWBTESA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- JWSMTBMIGYJJJM-UHFFFAOYSA-N magnesium;azane Chemical compound N.[Mg+2] JWSMTBMIGYJJJM-UHFFFAOYSA-N 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052585 phosphate mineral Inorganic materials 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/32—Details relating to UV-irradiation devices
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4618—Supplying or removing reactants or electrolyte
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Removal Of Specific Substances (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The embodiment of the invention discloses a kind of from containing the method reclaiming phosphorus fosfomycin waste water.The present invention utilizes the method that photoelectrocatalysioxidization oxidization works in coordination with di doped calcium；Graphite anode and stainless steel cathode are connected in photoelectrocatalysis reaction unit, and with uviol lamp as light source, the aqueous solution of NaCl is electrolyte；Under agitation, enter reaction unit containing fosfomycin waste water, porous hydrated calcium silicate is put into reaction unit simultaneously, control response voltage, temperature and time, monitor water quality index in real time, collect phosphorus after having reacted and reclaim product.During the recovery phosphorus of the present invention, energy consumption is low, and non-secondary pollution produces, and the product calcium hydroxy phosphate after recovery phosphorus can be used as phosphate fertilizer or phosphorus ore containing, achieves the efficient recovery of phosphor resource while processing polluted water.
Description
Technical field
The invention belongs to environmental project water treatment field, be specifically related to a kind of from containing the method reclaiming phosphorus fosfomycin waste water.
Background technology
Phosphorus is one of indispensable element of organism all cells, and phosphorus is also human genetic material nucleic acid and the key of energy conversion
The mankind and vegeto-animal various vital movement are had highly important effect by the important component of material adenosine triphosphate (ATP).
Phosphorus major part in biosphere is one-way flow, is a kind of non-renewable and irreplaceable precious resources.But, entirely
The phosphorus ore deposit of ball will at following century-old internal consumption totally.Therefore, from industry or agricultural production, phosphorus is the most effectively reclaimed
Resource, the hot issue paid close attention to the most both at home and abroad.
Fosfomycin antibiotic is one of widely used antibiotic.Fosfomycin water solublity is preferable, big after internal metabolism
Part is discharged with original shape, eventually enters into the sewage disposal system in city.It should be noted that various sewage disposal technology pair
Fosfomycin is inoperative or effect is the least.Therefore, fosfomycin is finally discharged in environment, to environment structure potential threat.
" Study on purification of fosfomycin sodium pharmacy waste water " (Northeastern University, Master's thesis, 2004.04) report with light electrolysis connection
Closing sequence written instructions activated sludge (SBR) method to process the waste water containing fosfomycin, this method is finally to discharge rich phosphorous sludge
Form phosphate is removed, and these mud contain substantial amounts of poisonous and harmful substance, it is difficult to be utilized effectively, this nothing
It is suspected to be that has blocked phosphor resource recycles approach, causes a large amount of losses of phosphor resource." a kind of high concentration phosphorus is mould for patent
The element process of pharmacy waste water and phosphorus recovery method " (application number: 201010293117) disclose and work in coordination with phosphorus with autoclave
The method that acid ammonium magnesium crystallization process reclaims phosphorus.But, high-temperature and high-pressure conditions can make this technology need higher energy consumption undoubtedly,
Further, since ammoniomagnesium phosphate crystal method needs sufficient magnesium source, for lacking the hinterland in magnesium source, this will certainly increase
Reclaim the cost of phosphorus.
Summary of the invention
In order to solve problem above, the invention provides a kind of from containing the method reclaiming phosphorus fosfomycin waste water.
It is a kind of from containing the method reclaiming phosphorus fosfomycin waste water that the present invention is supplied to, and comprises the following steps:
(1) graphite anode and stainless steel cathode are connected in photoelectrocatalysis reaction unit；Wherein, described photoelectrocatalysis
The light source of reaction unit is uviol lamp, and electrolyte is NaCl aqueous solution；
(2) start the agitating device of above-mentioned photoelectrocatalysis reaction unit, make to enter reaction unit containing fosfomycin waste water；With
Time by porous hydrated calcium silicate put into reaction unit, after react collect phosphorus recovery product.
Preferably, described a kind of from containing the method reclaiming phosphorus fosfomycin waste water, the rotating speed stirred described in step (2)
For 60-80r/min.
Preferably, described a kind of from containing the method reclaiming phosphorus fosfomycin waste water, porous aquation silicon described in step (2)
The dosage of acid calcium is 100-1000mg/L.
Preferably, described a kind of from containing the method reclaiming phosphorus fosfomycin waste water, wherein, described photoelectrocatalysis reaction unit
In response time be 10-15min.
Preferably, described a kind of from containing the method reclaiming phosphorus fosfomycin waste water, wherein, described photoelectrocatalysis reaction unit
In response voltage be 5-40V.
TiO2 Photocatalitic Technique of Semiconductor is a kind of environmentally-friendly technique, and it utilizes luminous energy degraded Organic Pollutants In Water to exist
Solve environmental pollution and energy shortage problem aspect shows huge application potential.After TiO2 photocatalyst is irradiated by light
Can produce electron-hole pair, wherein, hole has the strongest oxidability, it is possible to fosfomycin is degraded to orthophosphate.
But, there is a vital problem in this technology, that is, the electronics of generation and hole are easy to be combined, thus lead
The utilization ratio causing catalyst reduces.Graphite is a kind of material with photocatalytic activity and electric conductivity.If will
This material is as anode, while illumination, applies an electric field, can efficiently separate electronics and hole, so that phosphorus
Mycin can effectively be degraded to orthophosphate.
Porous hydrated calcium silicate be one can under the conditions of alkalescence (pH=8.0-9.0) spontaneous dissolving Ca2+And OH-'s
Material.Porous hydrated calcium silicate puts in the waste water containing fosfomycin, obtains orthophosphate also by photoelectrocatalysioxidization oxidization degraded
And be fixed up with the form of calcium hydroxy phosphate, thus reach to reclaim the purpose of phosphorus from fosfomycin waste water.
It is a kind of from containing the method reclaiming phosphorus fosfomycin waste water that the present invention provides, and is to process fosfomycin waste water and reclaim phosphorus
For the purpose of resource, photoelectrocatalysioxidization oxidization is utilized to work in coordination with the phosphorus recovery method of calcium hydroxy phosphate deposition.The present invention reclaims phosphorus
During energy consumption low, non-secondary pollution produces, and reclaim the product-calcium hydroxy phosphate after phosphorus can be as phosphate fertilizer or contain
Phosphate minerals is used, and achieves the efficient recovery of phosphor resource, have the advantages that while processing polluted water
1, produce light induced electron and hole by photocatalysis, additionally provide an electric field so that hole and electronics can have
Effect separates, and fosfomycin can be effectively degraded to orthophosphate by the hole with strong oxidizing property；
2, the electron transfer produced is to negative electrode, reacts generation hydroxyl (OH with water-), can be the formation of calcium hydroxy phosphate
Alkaline environment is provided, promotes the quick formation of calcium hydroxy phosphate；
3, porous hydrated calcium silicate can be with spontaneous dissolution Ca2+And OH-, Ca2+And OH-React with orthophosphate, in porous
The surface crystallization of hydrated calcium silicate forms calcium phosphate and the mixture of calcium hydroxy phosphate；After having reacted, phosphorus reclaims product-phosphorus
In the mixture of acid calcium and calcium hydroxy phosphate, the content (in terms of P) of phosphorus can reach 13%-15% (mass fraction),
This product can be used as phosphate fertilizer or phosphorus ore containing；
4, in course of reaction, producing without poisonous and harmful substance, the pH value of solution remains alkalescence (pH=7.5-9.0)；
After having reacted, detecting fosfomycin component content in water outlet is zero, PO4 3-Concentration is 3-5mg/L, COD concentration ＜ 50mg/L,
PH=7.5-8.5, water quality, without after-treatment, can directly be discharged.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, will make required in embodiment below
Accompanying drawing be briefly described, it should be apparent that, below describe in accompanying drawing be only some embodiments of the present invention, for
From the point of view of those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to obtain other according to these accompanying drawings
Accompanying drawing.
Fig. 1. the schematic diagram of photoelectrocatalysis reaction unit of the present invention；
1-water inlet；2-peristaltic pump；3-charging aperture；4-peristaltic pump；5 graphite anodes；6-stainless steel cathode；7-Constant Electric Current
Source；8-uviol lamp；9-mechanical agitation oar；10-outlet；11-discharging opening；
Fig. 2. in the embodiment of the present invention, phosphorus reclaims the XRD figure spectrum of product dominant phase；
Fig. 3. the phosphorus of the embodiment of the present invention 1 reclaims the FESEM figure of product appearance structure；
Fig. 4. the phosphorus of the embodiment of the present invention 1 reclaims the EDS of phosphorus content in product can spectrogram；
Fig. 5. the phosphorus of the embodiment of the present invention 2 reclaims the FESEM figure of product appearance structure；
Fig. 6. the phosphorus of the embodiment of the present invention 2 reclaims the EDS of phosphorus content in product can spectrogram；
Fig. 7. the phosphorus of the embodiment of the present invention 3 reclaims the FESEM figure of product appearance structure；
Fig. 8. the phosphorus of the embodiment of the present invention 3 reclaims the EDS of phosphorus content in product can spectrogram；
Fig. 9. the phosphorus of the embodiment of the present invention 4 reclaims the FESEM figure of product appearance structure；
Figure 10. the phosphorus of the embodiment of the present invention 4 reclaims the EDS of phosphorus content in product can spectrogram；
Figure 11. the phosphorus of the embodiment of the present invention 5 reclaims the FESEM figure of product appearance structure；
Figure 12. the phosphorus of the embodiment of the present invention 5 reclaims the EDS of phosphorus content in product can spectrogram；
Figure 13. the phosphorus of the embodiment of the present invention 6 reclaims the FESEM figure of product appearance structure；
Figure 14. the phosphorus of the embodiment of the present invention 6 reclaims the EDS of phosphorus content in product can spectrogram.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete retouching
State, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on the present invention
In embodiment, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise,
Broadly fall into the scope of protection of the invention.
The porous hydrated calcium silicate that the present invention is applied to, is prepared by following methods:
With CaO for and SiO2Respectively as calcareous and siliceous raw material, reference literature " preparation of porous hydrated calcium silicate and
Its phosphorus reclaims characteristic " (Research of Environmental Sciences, 2013,08), use dynamic autoclaved technology method, anti-at 110-170 DEG C
Answer and prepare under temperature conditions.
The present invention monitors water quality index in real time, and water quality index includes: fosfomycin concentration, phosphate concn (PO4 3-Concentration),
COD value and pH value.
Fosfomycin is by hplc determination；COD value uses potassium dichromate method to measure (GB11914-89)；Phosphate concn
By phosphomolybdic acid spectrophotometry (GB 11893-89)；PH value is measured by pH meter.
After measured, in the water outlet after the inventive method processes, fosfomycin content is zero, phosphate concn (PO4 3-
Concentration) it is 3-5mg/L, COD concentration ＜ 50mg/L, pH=7.5-8.5；Phosphorus reclaims the phosphorus content (in terms of P) in product
At 13%-15% (mass fraction).
The present invention is by field emission scanning electron microscope (FESEM), photoelectron spectroscopy (EDS) and X-ray diffraction (XRD)
Phosphorus is reclaimed product be analyzed.
Phosphorus reclaims shown in the appearance structure such as FESEM figure of product, and phosphorus reclaims the surface of product and covers lamellar and threadiness
Crystalline solid；In product shown in phosphorus content such as EDS figure；The dominant of phosphorus recovery product is as shown in XRD figure, and phosphorus returns
The dominant received in product is calcium phosphate and calcium hydroxy phosphate mutually.
Embodiment 1
(1) Fig. 1 is the schematic diagram of photoelectrocatalysis reaction unit of the present invention, first by graphite anode 5 and stainless
Steel negative electrode 6 is connected in the photoelectrocatalysis reaction unit that volume is 2L；Wherein, the light source of described photoelectrocatalysis reaction unit
For uviol lamp 8, power supply is constant current source 7, electrolyte be mass fraction be the NaCl aqueous solution of 0.5%, agitating device is
Mechanical agitation oar 9；
(2) response voltage arranging photoelectrocatalysis reaction unit is 5V, i.e. the voltage of constant current source 7 is 5V, ultraviolet light
Source is 5W, i.e. the power of uviol lamp 8 is 5W, speed of agitator 60r/min；Water quality containing fosfomycin waste water is fosfomycin
Concentration 1mg/L, COD value 1000mg/L, pH=7.5；Described entered by water inlet 1 through peristaltic pump 2 containing fosfomycin waste water
Reaction unit；Porous hydrated calcium silicate dosage is 100mg/L, enters by charging aperture 3 through peristaltic pump 4；Reaction temperature
It is 30 DEG C, response time 10min；React rear solution to flow out from outlet 10, sample tap has been set at outlet, real
Time monitoring water quality index, in discharging opening 11 collect phosphorus reclaim product.
Experimental result: after measured: in water outlet, fosfomycin content is zero, phosphate concn (PO4 3-Concentration) it is 3mg/L,
COD value is 10mg/L, pH=7.5；The phosphorus content (in terms of P) that phosphorus reclaims in product is 13% (mass fraction)；Phosphorus
Reclaim the appearance structure of product as shown in Figure 3, it is known that phosphorus reclaims the surface of product and covers lamellar and fibrous crystal material；
In product, phosphorus content is as shown in Figure 4；Phosphorus reclaims the dominant of product the most as shown in Figure 2, it is known that, phosphorus reclaims in product
Dominant is calcium phosphate and calcium hydroxy phosphate mutually.
Embodiment 2
(1) Fig. 1 is the schematic diagram of photoelectrocatalysis reaction unit of the present invention, first by graphite anode 5 and stainless
Steel negative electrode 6 is connected in the photoelectrocatalysis reaction unit that volume is 2L；Wherein, the light source of described photoelectrocatalysis reaction unit
For uviol lamp 8, power supply is constant current source 7, electrolyte be mass fraction be the NaCl aqueous solution of 2%, agitating device is machine
Tool stirring paddle 9；
(2) response voltage arranging photoelectrocatalysis reaction unit is 10V, i.e. the voltage of constant current source 7 is 10V, ultraviolet
Light source is 5W, i.e. the power of uviol lamp 8 is 5W, speed of agitator 70r/min；Water quality containing fosfomycin waste water is that phosphorus is mould
Element concentration 2mg/L, COD value 2000mg/L, pH=7.5；Described containing fosfomycin waste water through peristaltic pump 2 by water inlet 1
Enter reaction unit；Porous hydrated calcium silicate dosage is 200mg/L, enters by charging aperture 3 through peristaltic pump 4；Reaction
Temperature is 30 DEG C, response time 10min；React rear solution to flow out from outlet 10, sample tap be set at outlet,
Monitor water quality index in real time, collect phosphorus in discharging opening 11 and reclaim product.
Experimental result: after measured: in water outlet, fosfomycin content is zero, phosphate concn (PO4 3-Concentration) it is 3mg/L,
COD value is 12mg/L, pH=7.5；The phosphorus content (in terms of P) that phosphorus reclaims in product is 13.5% (mass fraction)；
Phosphorus reclaims the appearance structure of product as shown in Figure 5, it is known that phosphorus reclaims the surface of product and covers lamellar and fibrous crystal thing
Matter；In product, phosphorus content is as shown in Figure 6；Phosphorus reclaims the dominant of product the most as shown in Figure 2, it is known that, phosphorus reclaims product
In dominant be calcium phosphate and calcium hydroxy phosphate mutually.
Embodiment 3
(1) Fig. 1 is the schematic diagram of photoelectrocatalysis reaction unit of the present invention, first by graphite anode 5 and stainless
Steel negative electrode 6 is connected in the photoelectrocatalysis reaction unit that volume is 2L；Wherein, the light source of described photoelectrocatalysis reaction unit
For uviol lamp 8, power supply is constant current source 7, electrolyte be mass fraction be the NaCl aqueous solution of 2%, agitating device is machine
Tool stirring paddle 9；
(2) response voltage arranging photoelectrocatalysis reaction unit is 15V, i.e. the voltage of constant current source 7 is 15V, ultraviolet
Light source is 5W, i.e. the power of uviol lamp 8 is 5W, speed of agitator 70r/min；Water quality containing fosfomycin waste water is that phosphorus is mould
Element concentration 4mg/L, COD value 8000mg/L, pH=8.0；Described containing fosfomycin waste water through peristaltic pump 2 by water inlet 1
Enter reaction unit；Porous hydrated calcium silicate dosage is 300mg/L, enters by charging aperture 3 through peristaltic pump 4；Reaction
Temperature is 30 DEG C, response time 12min；React rear solution to flow out from outlet 10, sample tap be set at outlet,
Monitor water quality index in real time, collect phosphorus in discharging opening 11 and reclaim product.
Experimental result: after measured: in water outlet, fosfomycin content is zero, phosphate concn (PO4 3-Concentration) it is 4.2mg/L,
COD value is 34mg/L, pH=7.8；The phosphorus content (in terms of P) that phosphorus reclaims in product is 14.3% (mass fraction)；
Phosphorus reclaims the appearance structure of product as shown in Figure 5, it is known that phosphorus reclaims the surface of product and covers lamellar and fibrous crystal thing
Matter；In product, phosphorus content is as shown in Figure 6；Phosphorus reclaims the dominant of product the most as shown in Figure 2, it is known that, phosphorus reclaims product
In dominant be calcium phosphate and calcium hydroxy phosphate mutually.
Embodiment 4
(1) Fig. 1 is the schematic diagram of photoelectrocatalysis reaction unit of the present invention, first by graphite anode 5 and stainless
Steel negative electrode 6 is connected in the photoelectrocatalysis reaction unit that volume is 2L；Wherein, the light source of described photoelectrocatalysis reaction unit
For uviol lamp 8, power supply is constant current source 7, electrolyte be mass fraction be the NaCl aqueous solution of 2%, agitating device is machine
Tool stirring paddle 9；
(2) response voltage arranging photoelectrocatalysis reaction unit is 20V, i.e. the voltage of constant current source 7 is 20V, ultraviolet
Light source is 5W, i.e. the power of uviol lamp 8 is 5W, speed of agitator 80r/min；Water quality containing fosfomycin waste water is that phosphorus is mould
Element concentration 6mg/L, COD value 15000mg/L, pH=8.3；Described containing fosfomycin waste water through peristaltic pump 2 by water inlet 1
Enter reaction unit；Porous hydrated calcium silicate dosage is 500mg/L, enters by charging aperture 3 through peristaltic pump 4；Reaction
Temperature is 30 DEG C, response time 12min；React rear solution to flow out from outlet 10, sample tap be set at outlet,
Monitor water quality index in real time, collect phosphorus in discharging opening 11 and reclaim product.
Experimental result: after measured: in water outlet, fosfomycin content is zero, phosphate concn (PO4 3-Concentration) it is 4.5mg/L,
COD value is 42mg/L, pH=8.4；The phosphorus content (in terms of P) that phosphorus reclaims in product is 14.6% (mass fraction)；
Phosphorus reclaims the appearance structure of product as shown in Figure 7, it is known that phosphorus reclaims the surface of product and covers lamellar and fibrous crystal thing
Matter；In product, phosphorus content is as shown in Figure 8；Phosphorus reclaims the dominant of product the most as shown in Figure 2, it is known that, phosphorus reclaims product
In dominant be calcium phosphate and calcium hydroxy phosphate mutually.
Embodiment 5
(1) Fig. 1 is the schematic diagram of photoelectrocatalysis reaction unit of the present invention, first by graphite anode 5 and stainless
Steel negative electrode 6 is connected in the photoelectrocatalysis reaction unit that volume is 2L；Wherein, the light source of described photoelectrocatalysis reaction unit
For uviol lamp 8, power supply is constant current source 7, electrolyte be mass fraction be the NaCl aqueous solution of 2%, agitating device is machine
Tool stirring paddle 9；
(2) response voltage arranging photoelectrocatalysis reaction unit is 40V, i.e. the voltage of constant current source 7 is 40V, ultraviolet
Light source is 5W, i.e. the power of uviol lamp 8 is 5W, speed of agitator 80r/min；Water quality containing fosfomycin waste water is that phosphorus is mould
Element concentration 8mg/L, COD value 17000mg/L, pH=8.6；Described containing fosfomycin waste water through peristaltic pump 2 by water inlet 1
Enter reaction unit；Porous hydrated calcium silicate dosage is 800mg/L, enters by charging aperture 3 through peristaltic pump 4；Reaction
Temperature is 30 DEG C, response time 15min；React rear solution to flow out from outlet 10, sample tap be set at outlet,
Monitor water quality index in real time, collect phosphorus in discharging opening 11 and reclaim product.
Experimental result: after measured: in water outlet, fosfomycin content is zero, phosphate concn (PO4 3-Concentration) it is 4.8mg/L,
COD value is 45mg/L, pH=8.3；The phosphorus content (in terms of P) that phosphorus reclaims in product is 14% (mass fraction)；Phosphorus
Reclaim the appearance structure of product as shown in Figure 9, it is known that phosphorus reclaims the surface of product and covers lamellar and fibrous crystal material；
In product, phosphorus content is as shown in Figure 10；Phosphorus reclaims the dominant of product the most as shown in Figure 2, it is known that, phosphorus reclaims in product
Dominant is calcium phosphate and calcium hydroxy phosphate mutually.
Embodiment 6
(1) Fig. 1 is the schematic diagram of photoelectrocatalysis reaction unit of the present invention, first by graphite anode 5 and stainless
Steel negative electrode 6 is connected in the photoelectrocatalysis reaction unit that volume is 2L；Wherein, the light source of described photoelectrocatalysis reaction unit
For uviol lamp 8, power supply is constant current source 7, electrolyte be mass fraction be the NaCl aqueous solution of 2%, agitating device is machine
Tool stirring paddle 9；
(2) response voltage arranging photoelectrocatalysis reaction unit is 40V, i.e. the voltage of constant current source 7 is 40V, ultraviolet
Light source is 5W, i.e. the power of uviol lamp 8 is 5W, speed of agitator 80r/min；Water quality containing fosfomycin waste water is that phosphorus is mould
Element concentration 10mg/L, COD value 20000mg/L, pH=9.0；Described containing fosfomycin waste water through peristaltic pump 2 by water inlet 1
Enter reaction unit；Porous hydrated calcium silicate dosage is 1000mg/L, enters by charging aperture 3 through peristaltic pump 4；Reaction
Temperature is 30 DEG C, response time 15min；React rear solution to flow out from outlet 10, sample tap be set at outlet,
Monitor water quality index in real time, collect phosphorus in discharging opening 11 and reclaim product.
Experimental result: after measured: in water outlet, fosfomycin content is zero, phosphate concn (PO4 3-Concentration) it is 5mg/L,
COD value is 50mg/L, pH=8.5；The phosphorus content (in terms of P) that phosphorus reclaims in product is 15% (mass fraction)；Phosphorus
Reclaim the appearance structure of product as shown in figure 11, it is known that phosphorus reclaims the surface of product and covers lamellar and fibrous crystal material；
In product, phosphorus content is as shown in figure 12；Phosphorus reclaims the dominant of product the most as shown in Figure 2, it is known that, phosphorus reclaims in product
Dominant is calcium phosphate and calcium hydroxy phosphate mutually.
Claims (5)
1. one kind from containing the method reclaiming phosphorus fosfomycin waste water, it is characterised in that comprise the steps:
(1) graphite anode and stainless steel cathode are connected in photoelectrocatalysis reaction unit；Wherein, described photoelectrocatalysis
The light source of reaction unit is uviol lamp, and electrolyte is NaCl aqueous solution；
(2) start the agitating device of above-mentioned photoelectrocatalysis reaction unit, make to enter reaction unit containing fosfomycin waste water；With
Time by porous hydrated calcium silicate put into reaction unit, after react collect phosphorus recovery product.
A kind of from containing the method reclaiming phosphorus fosfomycin waste water, it is characterised in that step
(2) described in, the rotating speed of stirring is 60-80r/min.
A kind of from containing the method reclaiming phosphorus fosfomycin waste water, it is characterised in that step
(2) dosage of porous hydrated calcium silicate described in is 100-1000mg/L.
A kind of from containing the method reclaiming phosphorus fosfomycin waste water, it is characterised in that described
Response time in photoelectrocatalysis reaction unit is 10-15min.
A kind of from containing the method reclaiming phosphorus fosfomycin waste water, it is characterised in that described
Response voltage in photoelectrocatalysis reaction unit is 5-40V.
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| CN111847602A (en) * | 2020-06-12 | 2020-10-30 | 中国科学院生态环境研究中心 | Method for removing phosphorus by electrochemically regulating calcareous mineral material |
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| CN103979512A (en) * | 2014-05-21 | 2014-08-13 | 重庆文理学院 | Method for preparing crystals for recovering phosphorus |
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| CN103979512A (en) * | 2014-05-21 | 2014-08-13 | 重庆文理学院 | Method for preparing crystals for recovering phosphorus |
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| "多孔水化硅酸钙的制备及其磷回收特性";吉芳英等;《环境科学研究》;20130831;第26卷(第8期);第885页说明书摘要 * |
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