CN110002545A - A kind of dynamic membrane reactor and preparation method thereof for removing fluor in water - Google Patents
A kind of dynamic membrane reactor and preparation method thereof for removing fluor in water Download PDFInfo
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- CN110002545A CN110002545A CN201910429344.7A CN201910429344A CN110002545A CN 110002545 A CN110002545 A CN 110002545A CN 201910429344 A CN201910429344 A CN 201910429344A CN 110002545 A CN110002545 A CN 110002545A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000012528 membrane Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000919 ceramic Substances 0.000 claims abstract description 43
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 42
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 24
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 24
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 24
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical group [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 24
- 159000000007 calcium salts Chemical class 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000010452 phosphate Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 230000036961 partial effect Effects 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000003651 drinking water Substances 0.000 abstract description 10
- 235000020188 drinking water Nutrition 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 9
- 238000006115 defluorination reaction Methods 0.000 abstract description 6
- 241000894006 Bacteria Species 0.000 abstract description 3
- 241000195493 Cryptophyta Species 0.000 abstract description 3
- 108010034145 Helminth Proteins Proteins 0.000 abstract description 3
- 244000000013 helminth Species 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- 239000011737 fluorine Substances 0.000 description 13
- 229910052731 fluorine Inorganic materials 0.000 description 13
- 230000006872 improvement Effects 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910052587 fluorapatite Inorganic materials 0.000 description 5
- 229940077441 fluorapatite Drugs 0.000 description 5
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000035622 drinking Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 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 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 208000010501 heavy metal poisoning Diseases 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000002351 wastewater Substances 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Abstract
The dynamic membrane reactor and preparation method thereof that the present invention provides a kind of for removing fluor in water, the dynamic membrane reactor for removing fluor in water includes flat ceramic ultrafiltration membrane, the surface of the flat ceramic ultrafiltration membrane and its internal gutter are attached with dynamic film layer, and the dynamic film layer is calcium phosphate nanoparticles layer.Using technical solution of the present invention, defluorination effect is good, water stabilization, content of fluoride ion≤1 mg/L；Dynamic film layer can improve the filtering accuracy of ultrafiltration membrane, to the rejection effects of the substances such as bacterium, algae, helminth, silt in water better than individually using ultrafiltration membrance filter.It also can be reduced the generation of waste simultaneously and reduce processing difficulty, secondary pollution will not be caused to drinking water.Whole investment is low with operating cost, and ton cost of water treatment is low, and labor intensive is few, reduces processing cost.
Description
Technical field
The invention belongs to water-treatment technology field more particularly to a kind of dynamic membrane reactors and its system for removing fluor in water
Preparation Method.
Background technique
Fluorine is the essential trace elements of the human body, but the high water of people's long-term drinking fluorinated volume can damage tooth and bone, sternly
Weight can cause fluorosis of bone, and current high fluorinated water is widely distributed in China, influence people's health, China is drunk
Water hygiene standard provides that fluoride standard is 1.0mg/L.
Currently, the traditional approach of drinking water defluorination mainly uses lime precipitation, to remove the fluorine ion in drinking water, this
In the process along with Mg2+、Ca2+、Fe3+、Al3+With the precipitating and flocculation of sludge.It in addition to this, can also be by ion-exchange, anti-
The methods of osmosis and electrochemical process remove excessive fluorine ion in drinking water.However it is maximum in above method the disadvantage is that operation
Cost and maintenance cost are high, and can usually generate secondary pollution.Flocculent precipitation can simply and effectively remove the fluorine in water removal
Ion, however remaining fluorine ion is exceeded in water, is only applicable to high-concentration fluorine-containing waste water；Reverse osmosis membrane filtration method does not need other and adds
Add agent, however investment cost and processing cost are high, and film usually occur and be detached from or degrade；Electrochemical method equally exist installation and
The high problem of maintenance cost.
Absorption method is a kind of important physico-chemical process, because easy to operate, high-efficient, removable low concentration pollutant
Matter, obtains more application in Ca reservoir, adsorbent mainly have natural minerals adsorbent, metal oxide sorbents,
Biomass class adsorbent, houghite class adsorbent, ion exchange resin absorption and waste utilization adsorbent etc.；However absorption method
Need to handle largely discarded adsorbent material, post-treatment measure is a great problem.It is 5mg/L with fluorinion concentration, day output
For 100 tons of drink water purifying engineering, using activated alumina most mature at present as adsorbent, activated alumina
Practical fluorine ion adsorption capacity is 1-3mg/g, is the 1mg/L of standard by this drinking water treatment to fluorinion concentration, then daily
It at least needs to add 133kg activated alumina, is included in regenerated adsorption capacity and is also required to 60kg or so, and carry out regeneration and need to make
With acid-base solution, this process expends a large amount of manpower and water, the processing cost of water per ton about 2-5 member, in addition activated alumina meeting
Release Al3+, accumulation will lead to human body heavy metal poisoning throughout the year.
There is the method for the fluorine removal in conjunction with calcium phosphate using calcium carbonate in existing open source literature, fluorine removing rate 1.1mg/g,
It is suitable with the adsorption efficiency of activated alumina, but can not regenerate, same 3000 tons of fluorinion concentrations of processing are drinking for 5mg/L
Water will generate 15000kg waste, without clear superiority in cost and efficiency.And the adsorbance of hydroxyapatite is in 5-10mg/
L is 5 times of activated alumina or more, but the cost of hydroxyapatite is high, therefore only stays in the experimental stage, can not
It is promoted on a large scale.
Generally speaking, at present for drinking water without well be fluorine removing rate with higher, while waste again compared with
Few scheme.
Summary of the invention
Against the above technical problems, the invention discloses a kind of for the dynamic membrane reactor of removing fluor in water and its preparation side
Method improves treatment effeciency using the dynamic membrane reactor, reduces the generation of waste and reduces processing difficulty, is suitable for wide
The drink water purifying fluorine removal in large village area.
In this regard, the technical solution adopted by the present invention are as follows:
A kind of dynamic membrane reactor for removing fluor in water comprising flat ceramic ultrafiltration membrane, the flat ceramic ultrafiltration
The surface of film and its internal gutter are attached with dynamic film layer, and the dynamic film layer is calcium phosphate nanoparticles layer.Wherein, Dynamic Membrane
Layer has the function of that fluorine removal, ultrafiltration membrane and dynamic film layer play rejection effect jointly.
It adopts this technical solution, when for water fluoridation processing, calcium phosphate nanoparticles release PO in water4 3+And Ca2 +, PO4 3+、Ca2+With the F in water-Reaction generates the fluor-apatite of indissoluble, and the flat ceramic ultrafiltration membrane adopted this technical solution can be with
Fluor-apatite is retained, to achieve the purpose that fluorine removal, simultaneously because Dynamic Membrane can reduce the aperture of ultrafiltration membrane, improves filtering essence
Degree, thus this reactor is also greatly improved to the rejection effect of the substances such as bacterium, algae, helminth, silt in water.
As a further improvement of the present invention, so aperture≤100nm of the internal gutter of flat ceramic ultrafiltration membrane.
As a further improvement of the present invention, partial size >=50nm of the calcium phosphate nanoparticles.
As a further improvement of the present invention, the dynamic membrane reactor for removing fluor in water includes reaction vessel, institute
Reaction vessel is stated equipped with water inlet, water outlet, dosing mouth, the water outlet is connect with the water outlet of flat ceramic ultrafiltration membrane, institute
It states reaction vessel and is provided with raw water, the flat ceramic ultrafiltration membrane is immersed in water.
Further, the reaction vessel is equipped with agitating device.
Further, the lower part or bottom of the reaction vessel are equipped with mud discharging mouth.
The invention discloses a kind of preparation sides for the dynamic membrane reactor that removing fluor in water is used for described in any one as above
Method comprising following steps:
Flat ceramic ultrafiltration membrane is immersed in the water by step S1, and soluble phosphate and soluble calcium salt are put into water, is stirred
After mixing reaction, in water with the Surface Creation calcium phosphate nanoparticles of plate ceramic super-filtering film；
Step S2 runs the water-immersed flat ceramic ultrafiltration membrane, because flat ceramic ultrafiltration membrane is negative pressure
The surface of work principle of filter, the internal gutter that the calcium phosphate nanoparticles in water are attracted to flat ceramic ultrafiltration membrane forms internal filter
Cake layer is formed together Dynamic Membrane with the nano particle cake layer of flat ceramic ultrafiltration membrane surface attachment.
As a further improvement of the present invention, the soluble phosphate includes tertiary sodium phosphate, red sodium phosphate and phosphoric acid hydrogen
At least one of disodium.
As a further improvement of the present invention, the soluble calcium salt includes at least one in calcium chloride and calcium bicarbonate
Kind.
As a further improvement of the present invention, in step S1, the molar ratio of the soluble phosphate and soluble calcium salt
Meet n (PO4 3+): n (Ca2+)=2:3.00~3.15, and calcium salt is excessive.Calcium salt should be slightly excessive, guarantees remaining PO43 in water
+ and F- be lower than standard value.
As a further improvement of the present invention, in step S1, the mole of the soluble phosphate and soluble calcium salt
Meet n (PO with the mole of fluorine ion to be treated4 3+)+n(Ca2+)=(8.00~8.10) * n (F-)。
As a further improvement of the present invention, in step S1, PO in water4 3+Concentration be 0.8~1.3mol/L, Ca in water2+
Concentration be 1.2~2.0mol/L.I.e. after the amount of the phosphate and calcium salt added determines, by control the water of preset water come
The generation partial size for controlling calcium phosphate nanoparticles makes partial size >=50nm of the calcium phosphate nanoparticles generated.
Compared with prior art, the invention has the benefit that
Using technical solution of the present invention, defluorination effect is good, water stabilization, content of fluoride ion≤1mg/L；The drinking water removes
The defluorination effect of the dynamic membrane reactor of fluorine is relative to widely applied Defluorination of Formation Mater By Adsorption On Activated Alumina technology, moreover it is possible to reduce waste
Processing difficulty is generated and reduced, secondary pollution will not be caused to drinking water.Dynamic film layer can improve the filtering accuracy of ultrafiltration membrane, right
The rejection effect of the substances such as bacterium, algae, helminth, silt in water uses ultrafiltration membrance filter better than independent.Whole investment and fortune
Row is at low cost, and ton cost of water treatment is low, and labor intensive is few, reduces processing cost.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of dynamic membrane reactor for removing fluor in water of the invention.
Fig. 2 is the action principle figure of dynamic film layer of the invention.
Fig. 3 is the dynamic film layer local distribution structure chart inside ultrafiltration membrane surface and duct of the invention.
Appended drawing reference includes: 1- water inlet, 2- water outlet, 3- dosing mouth, 4- agitating paddle, 5- flat ceramic ultrafiltration membrane, 6-
Mud discharging mouth, 7- calcium phosphate nanoparticles layer, 8- internal gutter, 9- internal cake layer, 10- reaction vessel.
Specific embodiment
Illustrate the present invention With reference to embodiment, but these specific embodiments are only intended to illustrate this hair
It is bright, rather than limiting the invention.Those skilled in the art completely can under the inspiration of the present invention, to tool of the invention
Body embodiment or technical characteristic improve, but these still fall within protection of the invention by the technical solution improved or replaced
Range.
As shown in Figure 1, a kind of dynamic membrane reactor for removing fluor in water comprising reaction vessel 10, the reaction are held
Device 10 is equipped with water inlet 1, water outlet 2, the dosing mouth 3 for putting into soluble phosphate and soluble calcium salt, and the reaction is held
The built-in pending water of device 10, submergence has flat ceramic ultrafiltration membrane 5 in water；The water outlet 2 of the flat ceramic ultrafiltration membrane 5 with
The water outlet 2 of reaction vessel is connected by pipeline, is equipped with agitating paddle 4 in the reaction vessel 10, is immersed in the water；The reaction is held
The lower part of device 10 is equipped with mud discharging mouth 6.
As shown in Figures 2 and 3, the flat ceramic ultrafiltration membrane 5 includes internal gutter 8, the flat ceramic ultrafiltration membrane 5
Surface is attached with calcium phosphate nanoparticles layer 7 i.e. calcium phosphate dynamic film layer；The surface of the internal gutter 8 is attached with calcium phosphate and receives
The internal cake layer 9 that rice grain is constituted, the practical internal cake layer 9 is also dynamic film layer.
Further, so aperture≤100nm of the internal gutter 8 of flat ceramic ultrafiltration membrane 5.
Further, partial size >=50nm of the calcium phosphate nanoparticles.
The above-mentioned dynamic membrane reactor for removing fluor in water is prepared using following steps:
Flat ceramic ultrafiltration membrane is immersed in the water by step S1, and soluble phosphate and soluble calcium salt are put into water, is stirred
After mixing reaction, in water with the Surface Creation calcium phosphate nanoparticles of plate ceramic super-filtering film；
Step S2 runs the water-immersed flat ceramic ultrafiltration membrane, because ceramic membrane uses negative pressure filtration
The surface of working method, the internal gutter that the calcium phosphate nanoparticles for running Shi Shuizhong are attracted to flat ceramic ultrafiltration membrane is formed
Internal cake layer is formed together Dynamic Membrane with the nano particle cake layer of flat ceramic ultrafiltration membrane surface attachment.
Further, the soluble phosphate includes at least one in tertiary sodium phosphate, red sodium phosphate and disodium hydrogen phosphate
Kind.The soluble calcium salt includes at least one of calcium chloride and calcium bicarbonate.
Further, in step S1, the molar ratio of the soluble phosphate and soluble calcium salt meets n (PO4 3+): n
(Ca2+)=2:3.00~3.15, and calcium salt is excessive.Calcium salt should be slightly excessive, guarantees remaining PO4 in water3+And F-Lower than standard
Value.In step S1, the mole of the mole of the soluble phosphate and soluble calcium salt and fluorine ion to be treated is full
Sufficient n (PO4 3+)+n(Ca2+)=(8.00~8.10) * n (F-)。
Further, generation partial size, PO in water are controlled by adjusting the concentration of phosphate and calcium salt in preset water4 3+
Concentration be 0.8~1.3mol/L, Ca in water2+Concentration be 1.2~2.0mol/L.I.e. in the amount of the phosphate and calcium salt that add
After determination, the generation partial size of calcium phosphate nanoparticles is controlled by controlling the water of preset water.
It is further detailed below with reference to specific embodiment and comparative example.
Embodiment 1
By taking the drink water purifying engineering that fluorinion concentration is 5mg/L, day output is 100 tons as an example, the period is 30 days, is needed
The F of processing-Total amount is 789mol, by 20m2Ultrafiltration ceramic membrane immerses in the preset water of 2000L, and 2506mol is put into water
Disodium hydrogen phosphate and 3822mol calcium chloride, are stirred to react 4h, and in preset water and ceramic membrane surface production partial size is
The calcium phosphate nanoparticles of 160nm；Since the working method of ultrafiltration ceramic membrane is negative pressure filtration, ceramic membrane fortune
The surface that the calcium phosphate nanoparticles of row Shi Shuizhong will be adsorbed on ceramic membrane forms cake layer, and is grown in receiving for ceramic membrane surface
Rice grain forms Dynamic Membrane together.Calcium phosphate granules release PO4 in water3+And Ca2+, PO43+、Ca2+Encounter the F in water-It will
Reaction generates the fluor-apatite Ca of indissoluble5F(PO4)3, ultrafiltration ceramic membrane and Dynamic Membrane can retain fluor-apatite, to reach
To the purpose of fluorine removal, treated, and drinking water fluorinated volume is 0.8mg/L.3000 tons of drinking water of this period coprocessing expend medicament
1350 yuan, waste fluor-apatite 400kg is generated, the processing cost of ton water is about 0.5 yuan, and it is easy to operate, only need staff
Medicament and cleaning waste are periodically added, supervises and operates without continuous personnel, is suitable for the vast rural areas.
Comparative example 1
By taking the drink water purifying engineering that fluorinion concentration is 5mg/L, day output is 100 tons as an example, the period is 30 days, is needed
The F of processing-Total amount is 789mol, it is assumed that the practical fluorine ion adsorption capacity of activated alumina is 3mg/g meter, regenerates 3 times, then needs
7200 yuan of aluminium oxide or so are expended, needs to provide manpower and medicament when generating waste aluminium oxide 1800kg, and regenerating, operation is tired
Difficulty, the processing cost of ton water are about 2.5 yuan, and the adsorption capacity of activated alumina be less than 3mg/g when cost it is higher,
If regeneration times increase to two can also be down to processing cost 0.5 yuan more than ten times, but discharge Al after aluminium oxide regeneration repeatedly3+
Amount will increase, fluorine removing rate reduces, and operation so frequent is not particularly suited for the status of the vast rural areas.
By the comparison of embodiment 1 and comparative example 1 as it can be seen that the technical solution defluorination effect using the present embodiment 1 is good, water quality
Stablize, content of fluoride ion≤1mg/L；And investment is low with operating cost, ton cost of water treatment is low, and labor intensive is few.It reduces discarded
The generation of object simultaneously reduces processing difficulty.
Embodiment 2
Go out drinking original water with flat plate ultrafiltration membrane and Dynamic Membrane-ultrafiltration membrane respectively, compare its clean-up effect, as a result such as table 1
It is shown, it is seen that using the present embodiment 1 Dynamic Membrane and ultrafiltration membrane be used in combination after not only can fluorine removal, can also promote effluent quality,
The turbidity in water is significantly eliminated, microbial safety is greatly improved.
Table 1
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (9)
1. a kind of dynamic membrane reactor for removing fluor in water, it is characterised in that: it includes flat ceramic ultrafiltration membrane, the plate
The surface of ceramic super-filtering film and its internal gutter are attached with dynamic film layer, and the dynamic film layer is calcium phosphate nanoparticles layer.
2. the dynamic membrane reactor according to claim 1 for removing fluor in water, it is characterised in that: so flat ceramic is super
The aperture of the internal gutter of filter membrane≤100 nm.
3. the dynamic membrane reactor according to claim 1 for removing fluor in water, it is characterised in that: the calcium phosphate nano
The partial size of particle >=50 nm.
4. the dynamic membrane reactor of removing fluor in water is used for described in any one according to claim 1 ~ 3, it is characterised in that: described
Dynamic membrane reactor for removing fluor in water includes reaction vessel, and the reaction vessel is equipped with water inlet, water outlet, dosing mouth,
The water outlet is connect with the water outlet of flat ceramic ultrafiltration membrane, and the reaction vessel is provided with raw water, and the flat ceramic is super
Filter membrane is immersed in water.
5. a kind of preparation method of the dynamic membrane reactor for removing fluor in water as described in claim 1 ~ 4 any one,
It is characterized in that: the following steps are included:
Flat ceramic ultrafiltration membrane is immersed in the water by step S1, and soluble phosphate and soluble calcium salt are put into water, and stirring is anti-
Ying Hou, in water with the Surface Creation calcium phosphate nanoparticles of plate ceramic super-filtering film；
Step S2 runs the water-immersed flat ceramic ultrafiltration membrane, and the calcium phosphate nanoparticles in water are attracted to
The surface of the internal gutter of flat ceramic ultrafiltration membrane forms internal cake layer, the nanometer with the attachment of flat ceramic ultrafiltration membrane surface
Grain cake layer is formed together Dynamic Membrane.
6. the preparation method of the dynamic membrane reactor according to claim 5 for removing fluor in water, it is characterised in that: described
Soluble phosphate includes at least one of tertiary sodium phosphate, red sodium phosphate and disodium hydrogen phosphate.
7. the preparation method of the dynamic membrane reactor according to claim 6 for removing fluor in water, it is characterised in that: described
Soluble calcium salt includes at least one of calcium chloride and calcium bicarbonate.
8. the preparation method of the dynamic membrane reactor according to claim 6 for removing fluor in water, it is characterised in that: step
In S1, the molar ratio of the soluble phosphate and soluble calcium salt meets n(PO4 3+): n(Ca2+)=2:3.00 ~ 3.15, with need
The mole of fluorine ion to be processed meets n(PO4 3+)+n(Ca2+)=(8.00 ~ 8.10) * n(F-), and calcium salt is excessive.
9. the preparation method of the dynamic membrane reactor according to claim 5 for removing fluor in water, it is characterised in that: step
In S1, PO in water4 3+Concentration be 0.8 ~ 1.3 mol/L, Ca in water2+Concentration be 1.2 ~ 2.0 mol/L.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001259656A (en) * | 2000-03-16 | 2001-09-25 | Aquas Corp | Method for treating fluorine-containing waste water |
| CN101012082A (en) * | 2007-01-24 | 2007-08-08 | 大连理工大学 | Bioreactor using polyvinyl alcohol nano microsphere dynamic film as filtration medium |
| KR20070122269A (en) * | 2006-06-26 | 2007-12-31 | 경희대학교 산학협력단 | Method and apparatus for water treatment using dynamic membrane |
| CN101538028A (en) * | 2009-04-15 | 2009-09-23 | 中国科学院上海硅酸盐研究所 | Plate-like phosphoric acid calcium salt and preparation method and application thereof |
| CN102107938A (en) * | 2011-01-10 | 2011-06-29 | 中国科学技术大学苏州研究院 | Method for removing fluorine from water |
| CN102417273A (en) * | 2011-10-10 | 2012-04-18 | 北京建筑工程学院 | Dynamic membrane purifying reactor and method for removing ammonia nitrogen and organic matters from reclaimed water |
| CN105344314A (en) * | 2015-12-07 | 2016-02-24 | 上海绿强新材料有限公司 | Porous hollow tubular composite membrane and preparation method and application thereof |
| CN107935217A (en) * | 2017-11-24 | 2018-04-20 | 上海巴安水务股份有限公司 | A kind of waterborne radioactivity radium element removes system |
| CN108033534A (en) * | 2017-11-17 | 2018-05-15 | 江苏永冠给排水设备有限公司 | A kind of preparation method of fluorine removal solution and the technique for removing fluorine ion in water removal |
| CN109368742A (en) * | 2018-12-18 | 2019-02-22 | 北京建筑大学 | The method of extracellular polymeric recycling and removal of heavy metal ions in excess sludge |
| CN210001635U (en) * | 2019-05-22 | 2020-01-31 | 深圳中清环境科技有限公司 | dynamic membrane reactor for removing fluorine in water |
-
2019
- 2019-05-22 CN CN201910429344.7A patent/CN110002545A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001259656A (en) * | 2000-03-16 | 2001-09-25 | Aquas Corp | Method for treating fluorine-containing waste water |
| KR20070122269A (en) * | 2006-06-26 | 2007-12-31 | 경희대학교 산학협력단 | Method and apparatus for water treatment using dynamic membrane |
| CN101012082A (en) * | 2007-01-24 | 2007-08-08 | 大连理工大学 | Bioreactor using polyvinyl alcohol nano microsphere dynamic film as filtration medium |
| CN101538028A (en) * | 2009-04-15 | 2009-09-23 | 中国科学院上海硅酸盐研究所 | Plate-like phosphoric acid calcium salt and preparation method and application thereof |
| CN102107938A (en) * | 2011-01-10 | 2011-06-29 | 中国科学技术大学苏州研究院 | Method for removing fluorine from water |
| CN102417273A (en) * | 2011-10-10 | 2012-04-18 | 北京建筑工程学院 | Dynamic membrane purifying reactor and method for removing ammonia nitrogen and organic matters from reclaimed water |
| CN105344314A (en) * | 2015-12-07 | 2016-02-24 | 上海绿强新材料有限公司 | Porous hollow tubular composite membrane and preparation method and application thereof |
| CN108033534A (en) * | 2017-11-17 | 2018-05-15 | 江苏永冠给排水设备有限公司 | A kind of preparation method of fluorine removal solution and the technique for removing fluorine ion in water removal |
| CN107935217A (en) * | 2017-11-24 | 2018-04-20 | 上海巴安水务股份有限公司 | A kind of waterborne radioactivity radium element removes system |
| CN109368742A (en) * | 2018-12-18 | 2019-02-22 | 北京建筑大学 | The method of extracellular polymeric recycling and removal of heavy metal ions in excess sludge |
| CN210001635U (en) * | 2019-05-22 | 2020-01-31 | 深圳中清环境科技有限公司 | dynamic membrane reactor for removing fluorine in water |
Non-Patent Citations (1)
| Title |
|---|
| 沈世竑等: "《实用乡村医生手册》", 30 November 1995, 浙江科学技术出版社, pages: 101 * |
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