CN112456654B - Preparation method and application of biological seed crystal and method for synchronously removing calcium and fluorine in underground water - Google Patents
Preparation method and application of biological seed crystal and method for synchronously removing calcium and fluorine in underground water Download PDFInfo
- Publication number
- CN112456654B CN112456654B CN202011246138.1A CN202011246138A CN112456654B CN 112456654 B CN112456654 B CN 112456654B CN 202011246138 A CN202011246138 A CN 202011246138A CN 112456654 B CN112456654 B CN 112456654B
- Authority
- CN
- China
- Prior art keywords
- nutrient solution
- biological
- solution
- biological seed
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000013078 crystal Substances 0.000 title claims abstract description 51
- 239000011737 fluorine Substances 0.000 title claims abstract description 51
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011575 calcium Substances 0.000 title abstract description 41
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title abstract description 32
- 229910052791 calcium Inorganic materials 0.000 title abstract description 32
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title abstract 3
- 241000894006 Bacteria Species 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims description 97
- 235000015097 nutrients Nutrition 0.000 claims description 58
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 48
- 238000009630 liquid culture Methods 0.000 claims description 30
- 239000010802 sludge Substances 0.000 claims description 30
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 14
- 238000012258 culturing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000003124 biologic agent Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 239000011573 trace mineral Substances 0.000 claims description 11
- 235000013619 trace mineral Nutrition 0.000 claims description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000011775 sodium fluoride Substances 0.000 claims description 7
- 235000013024 sodium fluoride Nutrition 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 6
- 230000001580 bacterial effect Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000002068 microbial inoculum Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000003673 groundwater Substances 0.000 abstract description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 12
- 238000001556 precipitation Methods 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 6
- 244000005700 microbiome Species 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000001963 growth medium Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 238000002156 mixing Methods 0.000 description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 230000000415 inactivating effect Effects 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000669298 Pseudaulacaspis pentagona Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- GFIKIVSYJDVOOZ-UHFFFAOYSA-L calcium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Ca+2].[O-]P([O-])(F)=O GFIKIVSYJDVOOZ-UHFFFAOYSA-L 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000001490 effect on brain Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical class [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 210000002569 neuron Anatomy 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000011218 seed culture Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000003313 weakening effect 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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
-
- 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
-
- 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
- C02F2103/06—Contaminated groundwater or leachate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention discloses a preparation method and application of biological seed crystals and a method for synchronously removing calcium and fluorine in groundwater. The invention provides a method for synchronously removing fluorine and calcium pollutants in underground water by using biological seed crystals with bacteria as cores under the adsorption action and the induced precipitation action. Solves the problem of exogenous organic matters in the application of microorganism-induced calcium carbonate precipitation, and avoids the safety risk of microorganisms in effluent. The invention induces the formation of biological seed crystal by bacteria, and the seed crystal is taken out in the initial stage of nucleation to prepare the biological seed crystal.
Description
Technical Field
The invention belongs to the technical field of groundwater treatment, and particularly relates to a method for removing calcium and fluorine pollutants in groundwater by using biological seed crystals.
Background
Excessive fluoride uptake can lead to changes in enamel, leading to staining and pitting. Fluoride may concentrate in bone, thereby stimulating the growth of bone cells, altering the structure of various tissues and eventually weakening the bone. Even more serious, drinking water containing high concentrations of fluoride can have an effect on brain and nerve cells, resulting in other adverse health effects, including damage to non-skeletal tissues of the kidney, reproductive and digestive systems. In addition, the fluorine pollution of the underground water can poison animals and plants, and the production of agriculture and animal husbandry is affected. For industry and households, excessive hardness in water can cause fouling problems in equipment, pipelines, storage tanks, etc. When city citizens drink tap water, due to the existence of high hardness, a large amount of white scale can appear after boiling water which originally meets the drinking requirement, and a plurality of damages such as sense discomfort and the like exist.
The prior technology for removing fluoride in groundwater mainly comprises the following steps: electrodialysis, reverse osmosis, nanofiltration, adsorption, bioadsorption, nalgonda technology, ion exchange. The removal processes have the advantages of no need of medium, high absorption capacity, easy obtainment of corresponding chemical products and the like. However, the major drawbacks associated with these processes are high operating costs, large amounts of waste such as water desalination, excessive hydraulic and electrical power consumption, and disposal of the resulting waste. These physicochemical methods are instead ineffective or expensive when the fluoride ion contaminant concentration is very low. The hardness removal technology commonly used in groundwater mainly comprises: a chemical softening method based on the solubility product principle and an ion exchange softening method based on the ion exchange principle. In addition, as membrane separation technology has been developed, reverse osmosis technology has become one of the main measures for softening groundwater. The technology has the advantages of simple method, obvious effect, high removal rate, good effluent quality and the like, but also has the problems of high operation cost and severe operation condition requirements. The invention adopts biological seed crystal to induce precipitation, and compared with chemical precipitation using lime and calcium salt, the induced crystallization has obvious advantages. The bio-seed material may promote crystallization and then precipitate with the attached crystals, which may significantly shorten the reaction time.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for synchronously removing fluorine and calcium pollutants in underground water by using biological seed crystals with bacteria as cores under the adsorption action and the induced precipitation action. Solves the problem of exogenous organic matters in the application of microorganism-induced calcium carbonate precipitation, and avoids the safety risk of microorganisms in effluent.
In order to realize the technical task, the invention adopts the following technical scheme:
a method for preparing a biological seed, the method comprising the steps of:
step one, enrichment culture of sludge: obtaining a mud-water mixture from underground water, adding a nutrient solution I into the mud-water mixture, carrying out enrichment culture on the mud-water mixture added with the nutrient solution I under a constant-temperature aerobic condition, and collecting enriched sludge;
step two, preparation of biological bacteria: adding a nutrient solution I into the collected enriched sludge, performing constant-temperature culture, and collecting a biological bacterial agent precipitate;
step three, preparing biological seed crystals: the biological agent and the nutrient solution II obtained in the second step are mixed according to the mass ratio of 1:7-20, culturing under constant-temperature aerobic condition, precipitating, separating, washing, drying, and sieving to obtain biological seed crystal;
the formula of the nutrient solution I is as follows:
C 4 H 4 Na 2 O 4 ·6H 2 O：0.8-1.2g/L ，NaNO 3 ：0.08-0.12g/L，NaHCO 3 ：0.8-1.2g/L，CaCl 2 :0.4-0.6g/L and 0.0075-0.0125 g/L of trace elements;
the formula of the nutrient solution II is as follows:
C 4 H 4 Na 2 O 4 ·6H 2 O：0.4-0.6g/L ，NaNO 3 ：0.08-0.12g/L，NaHCO 3 ：0.4-0.6g/L，KH 2 PO 4 ：0.04-0.06g/L，MgCl 2 ：0.04-0.06 g /L，CaCl 2 :0.4-0.6g/L and 0.0075-0.0125 g/L of trace elements.
The saidThe preferred formula of nutrient solution I is as follows: c (C) 4 H 4 Na 2 O 4 ·6H 2 O：0.8-1.2g/L ，NaNO 3 ：0.08-0.12g/L，NaHCO 3 ：0.8-1.2g/L，KH 2 PO 4 ：0.04-0.06g/L，MgCl 2 ：0.04-0.06 g/L，CaCl 2 :0.4-0.6g/L and 0.0075-0.0125 g/L of trace elements.
Further, the microelements comprise the following raw materials in percentage by mass:
EDTA：0.8-1.2g/L， ZnSO 4： 0.4-0.6g/L，MnCl 2 ·4H 2 O：0.1-0.3g/L ，MgSO 4 ·7H 2 O：0.4-0.6g/L，CuSO 4 ·5H 2 O：0.4-0.6g/L ，CoCl 2 ·6H 2 O：0.1-0.3g/L ，FeSO 4 ·7H 2 o:0.4-0.6g/L, ph=7.0.
Preferably, the mud-water mixture and the nutrient solution I are uniformly mixed according to the mass ratio of 2-4:1.
Further, the sludge enrichment culture comprises the following steps: firstly, adding 1-3mg/L sodium fluoride solution into a mud-water mixture obtained from underground water, replacing half of supernatant liquid with nutrient solution I, carrying out enrichment culture for 7-10 days, and oscillating 3-4 times per day by adopting a shaking table with the rotating speed of 30-60 rpm for 10-15 minutes each time; secondly, adding sodium fluoride solution with concentration 200% -600% higher than that of the first step, and partially replacing the nutrient solution I in the last step; and thirdly, repeating the second step until the fluorine removal rate in the liquid culture solution reaches over 70 percent, and finishing sludge enrichment.
Further, the preparation of the biological agent comprises the following steps: firstly, adding a nutrient solution I into enriched sludge, wherein the enriched sludge and the nutrient solution I are mixed according to the mass ratio of 1:100-150, and culturing at a constant temperature of 25-30 ℃; step two, replacing the liquid culture solution once every other period, wherein the liquid culture solution is nutrient solution I and sterilized underground water according to the volume ratio of 1: 1-3, wherein the concentration of the nutrient solution I of the liquid culture solution which is replaced successively is reduced in sequence; until the bottom of the underground water is deep black and is in a bulk sludge state, and the fluorine removal rate in the liquid culture solution is measured to be more than 70%, the preparation of the biological microbial inoculum is completed.
Further, the preparation of the biological seed crystal specifically comprises: the microbial inoculum sediment and the nutrient solution II obtained in the second step are mixed according to the mass ratio of 1:7-20, culturing at a vibration speed of 160-180 r/min by a constant temperature oscillator under aerobic condition with a temperature of 30-35 ℃ for 24-36h, treating the mixed solution with ultrasonic waves for 8-15 min, taking out small biological precipitate particles generated on the culture substrate, separating with a centrifuge, repeatedly washing biological seed crystal with deionized water to remove soluble impurities, drying at 60 ℃ for 24 h, and sieving to form powder to obtain the biological seed crystal.
The biological seed crystal provided by the invention can be applied to synchronously removing calcium and fluorine in underground water.
The invention further discloses a method for synchronously removing calcium and fluorine in underground water, which comprises the following steps:
the first step: the treated water flows into a mixing reactor, biological seed crystals prepared according to the claims 1-5 are added into the reactor, the adding amount of the biological seed crystals is 1-2 g/L, and the temperature is kept at 25+/-2 ℃;
in the second step, ca is added into water 2+ :F - When the mass concentration is more than 60-150, the mixing reaction time is 5-3 hours, and when Ca is added into water 2+ :F - When the mass concentration is 10-60, the mixing reaction time is 7-5 hours; when the concentration of calcium ions in the solution is lower than 30mg/L, calcium chloride is required to be supplemented to the bottom of the mixing reactor until the concentration of calcium ions reaches 30mg/L.
Meanwhile, in order to improve the practical application value of the technical content of the invention, the invention also provides a mixing reactor for synchronously removing calcium and fluorine in underground water, wherein the mixing reactor at least comprises a water inlet and a water outlet, and the inside of the mixing reactor container is filled with the biological seed crystal prepared by the method.
Preferably, a stirrer is also arranged in the mixing reactor, and the rotating speed of the stirrer is 100-150r/min.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention is generalThe formation of biological seed crystals is induced by the bacteria, which seed crystals are removed in the initial stage of nucleation (cultivation for 36-48 h) to produce biological seed crystals, which are then added to a seed culture medium containing the seed crystals of F - And Ca 2+ In the polluted groundwater, fluorine and calcium ions in the water body are successfully removed through adsorption and crystallization nucleation.
(2) The invention utilizes the crystal induced crystallization synthesized by microorganism induced calcium carbonate precipitation (MICP) as a high-efficiency fluorine adsorbent, and provides a cleaner and more economical alternative way for breaking through the application limit of MICP in groundwater. The problem of foreign organic matters in the application of microorganism-induced calcium carbonate precipitation is solved, and the microbial safety risk of effluent is avoided.
(3) The biological seed crystal adopted by the invention for treating the groundwater has the characteristics of high surface porosity and large specific surface area, is an economic and environment-friendly adsorbent, and can be used for removing fluorine from the groundwater. Calcium fluorophosphate is formed in the process of removing fluorine, so that the method has the effect of removing phosphorus and calcium.
(4) The invention adopts biological seed crystal adsorption and induced precipitation, and compared with chemical precipitation using lime and calcium salt, induced crystallization has obvious advantages. The seed material may promote crystallization and then precipitate with the attached crystals, which may significantly shorten the reaction time, since induced crystallization is performed on the seed material, and thus no fine precipitate is produced that is difficult to remove.
Drawings
FIG. 1 is a diagram of a process for forming a biological seed crystal in accordance with the present invention; wherein FIG. 1 (a) shows a biological agent cultured for 36 h; (b) before biological seed addition; (c) scanning electron micrographs after the biological crystal reaction.
FIG. 2 shows the fluorine removal results of example 1 of the present invention.
FIG. 3 shows the results of the calcium removal of example 1 of the present invention.
FIG. 4 shows the fluorine removal results of example 2 of the present invention.
FIG. 5 shows the results of the calcium removal of example 2 of the present invention.
FIG. 6 shows the fluorine removal results of example 3 of the present invention.
FIG. 7 shows the results of the calcium removal of example 3 of the present invention.
The invention is described in further detail below with reference to the drawings and detailed description. The following description is of the preferred embodiment of the invention and is not intended to limit the invention to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Detailed Description
The whole technical conception of the invention is based on the following technical mechanism:
Cell+Ca 2+ =Cell-Ca 2+ (Process of calcium-precipitating bacteria attracting calcium ions)
Cell-Ca 2+ + CO 3 2- =Cell-CaCO 3 (Process of calcium precipitation bacteria inducing calcium carbonate precipitation)
CaCO 3 +2F - +H + =CaF 2 +HCO 3 - (ion exchange process of calcium carbonate with fluoride ion adsorbed on its surface)
Ca 5 (PO 4 ) 3 OH+F - =Ca 5 (PO 4 ) 3 F+OH - (substitution of hydroxyl groups by fluoride ions)
Ca 2+ +2F - →CaF 2 (precipitation of free calcium and fluoride)
5Ca 2+ +F - +3PO 4 3- →Ca 5 (PO 4 ) 3 F (Co-precipitation of calcium, phosphate and fluoride)
Through the reaction, the simultaneous removal of fluorine and calcium in the underground water is realized.
Example 1
Following the overall technical concept of the present invention, the groundwater to be treated in embodiment 1 is self-service groundwater from a farmer in a village in Changan area of western An, shaanxi, and includes the following steps:
step one, enrichment culture of sludge:
10L of muddy water is obtained from a reservoir or a sewage plant as a bacterial source, and the nutrient solution I is taken as a domestication culture medium, wherein the mass ratio is 3:1 are mixed evenly and placed in 200ml conical flasks, and are enriched and cultivated in a constant temperature incubator (at 27 ℃) under aerobic conditions. In the enrichment culture process, 7 days are taken as a culture period, sodium fluoride with different concentrations (fluorine concentration is 1, 3 and 5 mg/L) is added into a conical flask in each period, and the conical flask is kept stand, and half of supernatant is replaced to be nutrient solution I; in the enrichment process, a shaking table with the rotating speed of 40 turns is adopted, shaking is carried out 3 times a day for 15 minutes each time, and nutrient substances for bacteria to grow are ensured to be in the reactor. After each enrichment period is enriched for 3 weeks, the fluorine removal rate is measured to be 75.95%, which indicates that enrichment and domestication are completed;
the formula of the enriched nutrient solution I in the step one is as follows:
nutrient solution I (nutrient solution for screening calcium-precipitating bacteria) comprises the following components in percentage by mass:
C 4 H 4 Na 2 O 4 ·6H 2 O：0.8g/L ，NaNO 3 ：0.08g/L，NaHCO 3 ：0.8g/L
CaCl 2 :0.4g/L and trace elements 0.0075-0.0125 g/L
Wherein the microelements comprise the following raw materials in percentage by mass: EDTA:0.8g/L, znSO 4 ：0.4g/L，MnCl 2 ·4H 2 O：0.1g/L，MgSO 4 ·7H 2 O：0.4g/L ，CuSO 4 ·5H 2 O：0.4g/L ，CoCl 2 ·6H 2 O：0.1g/L ，FeSO 4 ·7H 2 O:0.4g/L, ph=7.0.
Step two, preparation of biological bacteria:
collecting the enriched sludge in the enrichment conical flask, and adding a nutrient solution I into the enriched sludge to obtain a mixture of 1:150 in 200ml conical flask, placing the conical flask into a constant temperature shaking incubator for culturing for 3 days at 27 ℃, and then replacing liquid culture solution every 3 days, wherein the liquid culture solution is culture solution I and sterilized underground water according to the volume ratio of 1: 1-3, wherein the replacement sequence is as follows: nutrient solution I and sterilized groundwater are prepared from 1:1 proportion of liquid culture medium, nutrient solution I and sterilized underground water, wherein the liquid culture medium, the nutrient solution I and the sterilized underground water are prepared from the following components in percentage by weight: 2, the liquid culture medium, the nutrient solution I and the sterilized groundwater are composed of 1:3 proportion of liquid culture medium. Deep black and scattered sludge is formed at the bottom of underground water, and the fluorine removal rate in the liquid culture solution is measured to be 78.65%, which indicates that the biological agent is successfully prepared;
step three, preparing biological seed crystals:
mixing the biological agent obtained in the second step with the nutrient solution II in a proportion of 10% in a 250ml conical flask, sealing the conical flask by using a sealing film, and culturing at a vibration speed of 180 revolutions per minute on a constant temperature vibrator under an aerobic condition at a temperature of 30 ℃. After 36h of incubation, the solution was sonicated for 10 minutes. Taking out small particles of biological sediment generated on the culture substrate, separating with a centrifuge at 8000 rpm for 15min, repeatedly washing biological seed crystal with deionized water to remove soluble impurities, inactivating bacteria at this time, drying the sample at 60deg.C for 24 hr, sieving with 100 sieve to obtain powder, and finally forming biological seed crystal.
The formula of the enriched nutrient solution II in the step three is as follows (in terms of mass concentration):
C 4 H 4 Na 2 O 4 ·6H 2 O：0.4g/L ，NaNO 3 ：0.08g/L，NaHCO 3 ：0.4g/L
KH 2 PO 4 ：0.04g/L，MgCl 2 ：0.04 g /L，CaCl 2 :0.4g/L and 0.0075-0.0125 g/L of trace elements.
Wherein the microelements comprise the following raw materials in percentage by mass:
EDTA：0.8g/L，ZnSO 4 ：0.4g/L，MnCl 2 ·4H 2 O：0.1g/L，MgSO 4 ·7H 2 O：0.4g/L ，CuSO 4 ·5H 2 O：0.4g/L ，CoCl 2 ·6H 2 O：0.1g/L ，FeSO 4 ·7H 2 o:0.4g/L, ph=7.0.
Further, the method for synchronously removing calcium and fluorine in the underground water comprises the following steps:
first, the process water flows into the mixing reactor. After charging, biological seed crystal is added into the reactor with the addition amount of 1 g/L, and the reactor enters a treatment stage, wherein the temperature is 25 ℃ and the rotating speed is 100r/min. And (3) standing for 20min after stirring is finished, discharging the supernatant after the treatment, and then re-carrying out water inflow of the second round. The reaction time was set to 4 hours. This example was supplemented with 2.5mg/L of fluorine to meet the initial fluorine concentration for optimal adsorption efficiency.
As can be seen from fig. 2 and 3, the efficiency of removing fluorine and calcium in the initial operation period of the reactor is lower, the efficiency of removing fluorine and calcium in the reactor is gradually increased along with the extension of time, the fluorine removal rate of the reactor in the stationary phase can reach 83.06%, the calcium removal rate reaches 75.85%, and the reactor shows good capability of removing fluorine and calcium.
Example 2
Following the overall technical concept of the present invention, the groundwater to be treated in example 2 is derived from the groundwater used in a village in yi district of western security, shanxi province, and comprises the following steps:
step one, enrichment culture of sludge:
10L of muddy water is obtained from a reservoir or a sewage plant as a bacterial source, and the nutrient solution I is taken as a domestication culture medium, wherein the mass ratio is 3:1 are mixed evenly and placed in 200ml conical flasks, and are enriched and cultivated in a constant temperature incubator (at 27 ℃) under aerobic conditions. In the enrichment culture process, 7 days are taken as a culture period, sodium fluoride with different concentrations (fluorine concentration is 1, 2 and 4 mg/L) is added into a conical flask in each period, and the conical flask is kept stand, and half of supernatant is replaced to be nutrient solution I; in the enrichment process, a shaking table with the rotating speed of 40 turns is adopted, shaking is carried out 3 times a day for 15 minutes each time, and nutrient substances for bacteria to grow are ensured to be in the reactor. After 3 weeks of enrichment in each enrichment cycle, the fluorine removal rate was measured to be 78.45%, indicating that the enriched sludge acclimation was complete.
The formula of the enriched nutrient solution I in the step one is as follows:
nutrient solution I (nutrient solution for screening calcium-precipitating bacteria) comprises the following components in percentage by mass:
C 4 H 4 Na 2 O 4 ·6H 2 O：1.2g/L ，NaNO 3 ：0.12g/L，NaHCO 3 ：1.2g/L
KH 2 PO 4 ：0.06g/L，MgCl 2 ：0.06 g/L ，CaCl 2 :0.6g/L and 0.0075-0.0125 g/L of trace elements;
wherein the microelements comprise the following raw materials in percentage by mass: : EDTA:1.2g/L, znSO 4 ：0.6g/L ，MnCl 2 ·4H 2 O：0.3g/L ，MgSO 4 ·7H 2 O：0.6g/L ， CuSO 4 ·5H 2 O：0.6g/L， CoCl 2 ·6H 2 O：0.3g/L，FeSO 4 ·7H 2 O:0.6g/L, ph=7.0.
Step two, preparation of biological bacteria:
collecting the enriched sludge in the enrichment conical flask, and adding a culture solution I into the enriched sludge to obtain a mixture of 1:100 in 200ml conical flask, placing the conical flask into a constant temperature shaking incubator for culturing for 3 days at 27 ℃, and then replacing liquid culture solution every 3 days, wherein the liquid culture solution is culture solution I and sterilized underground water according to the volume ratio of 1: 1-3, wherein the replacement sequence is as follows: culture solution I and sterilized groundwater consist of 1:1 proportion of liquid culture medium, culture solution I and sterilized underground water, wherein the liquid culture medium, the culture solution I and the sterilized underground water are prepared from the following components in percentage by weight: 1.5 ratio of liquid culture medium, culture solution I and sterilized groundwater consisting of 1:2.5 ratio of liquid medium. Deep black and scattered sludge is formed at the bottom of underground water, and the fluorine removal rate in the liquid culture solution is 79.55% by measurement, so that the biological agent is successfully prepared;
step three, preparing biological seed crystals:
mixing the biological agent obtained in the second step with the nutrient solution II in a proportion of 10% in a 250ml conical flask, sealing the conical flask by using a sealing film, and culturing at a vibration speed of 180 revolutions per minute on a constant temperature vibrator under an aerobic condition at a temperature of 30 ℃. After 36h of incubation, the solution was sonicated for 10 minutes. Taking out small particles of biological sediment generated on the culture substrate, separating with a centrifuge at 8000 rpm for 15min, repeatedly washing biological seed crystal with deionized water to remove soluble impurities, inactivating bacteria at this time, drying the sample at 60deg.C for 24 hr, sieving with 100 sieve to obtain powder, and finally forming biological seed crystal with bacteria as core.
The formula of the enriched nutrient solution II in the step three is as follows (in terms of mass concentration):
C 4 H 4 Na 2 O 4 ·6H 2 O：0.6g/L ，NaNO 3 ：0.12g/L，NaHCO 3 ：0.6g/L
KH 2 PO 4 ：0.06g/L，MgCl 2 ：0.06 g /L，CaCl 2 :0.6g/L and 0.0075-0.0125 g/L of trace elements.
Wherein the microelements comprise the following raw materials in percentage by mass: : EDTA:1.2g/L, znSO 4 ：0.6g/L ，MnCl 2 ·4H 2 O：0.3g/L ，MgSO 4 ·7H 2 O：0.6g/L ， CuSO 4 ·5H 2 O：0.6g/L， CoCl 2 ·6H 2 O：0.3g/L，FeSO 4 ·7H 2 O:0.6g/L, ph=7.0.
The method for synchronously removing calcium and fluorine in the underground water comprises the following specific steps of:
first, the process water flows into the mixing reactor. After charging, biological seed crystals are added into the reactor, the adding amount is 1.5/g/L, the reactor enters a treatment stage, the temperature is 25 ℃, and the rotating speed is 100r/min. And (3) standing for 20min after stirring is finished, discharging the supernatant after the treatment, and then re-carrying out water inflow of the second round. The reaction time was set to 4 hours. The initial fluorine concentration of 2.69mg/L was supplemented to satisfy the optimum adsorption efficiency, and the present example supplemented with 2.69mg/L to satisfy the optimum adsorption efficiency.
As can be seen from figures 4 and 5, the efficiency of fluorine and calcium removal in the initial operation stage of the reactor is lower, the efficiency of fluorine and calcium removal in the reactor is gradually increased along with the extension of time, the fluorine removal rate of the reactor in the steady period can reach 82.96%, the calcium removal rate reaches 74.45%, and the better fluorine and calcium removal capability is shown.
Example 3
Following the overall technical concept of the present invention, embodiment 3 of groundwater to be treated is from private groundwater of a village in Changan district of western Ann, shaanxi, and includes the following steps:
step one, enrichment culture of sludge:
10L of muddy water is obtained from a reservoir or a sewage plant as a bacterial source, and the nutrient solution I is taken as a domestication culture medium, wherein the mass ratio is 3:1 are mixed evenly and placed in 200ml conical flasks, and are enriched and cultivated in a constant temperature incubator (at 27 ℃) under aerobic conditions. In the enrichment culture process, 7 days are taken as a culture period, sodium fluoride with different concentrations (fluorine concentration is 1, 2.5 and 3.5 mg/L) is added into a conical flask in each period, and the conical flask is kept stand, and half of supernatant is replaced to be nutrient solution I; in the enrichment process, a shaking table with the rotating speed of 40 turns is adopted, shaking is carried out 3 times a day for 15 minutes each time, and nutrient substances for bacteria to grow are ensured to be in the reactor. After each enrichment period is enriched for 3 weeks, the fluorine removal rate is measured to be 78.88%, which indicates that enrichment and domestication are completed;
the formula of the enriched nutrient solution I in the step one is as follows:
nutrient solution I (nutrient solution for screening calcium-precipitating bacteria) comprises the following components in percentage by mass:
C 4 H 4 Na 2 O 4 ·6H 2 O：1.0g/L ，NaNO 3 ：0.1g/L，NaHCO 3 ：1.0g/L
KH 2 PO 4 ：0.04g/L，MgCl 2 ：0.04 g/L ，CaCl 2 :0.5g/L and 0.0075-0.0125 g/L of trace elements;
wherein the microelements comprise the following raw materials in percentage by mass:
EDTA：1.0g/L， ZnSO 4 ：0.5g/L， MnCl 2 ·4H 2 O：0.2g/L， MgSO 4 ·7H 2 O：0.5g/L，CuSO 4 ·5H 2 O：0.5g/L ， CoCl 2 ·6H 2 O：0.2g/L，FeSO 4 ·7H 2 o:0.5g/L, ph=7.0.
Step two, preparation of biological bacteria:
and collecting the enriched sludge in the enriched conical flask. Adding a culture solution I into the enriched sludge, wherein the ratio of the culture solution I to the enriched sludge is 1:100 in 200ml conical flask, placing the conical flask into a constant temperature shaking incubator for culturing for 3 days at 27 ℃, and then replacing liquid culture solution every 3 days, wherein the liquid culture solution is culture solution I and sterilized underground water according to the volume ratio of 1: 1-3, wherein the replacement sequence is as follows: culture solution I and sterilized groundwater consist of 1:1 proportion of liquid culture medium, culture solution I and sterilized underground water, wherein the liquid culture medium, the culture solution I and the sterilized underground water are prepared from the following components in percentage by weight: 1.5 ratio of liquid culture medium, culture solution I and sterilized groundwater consisting of 1:3 proportion of liquid culture medium. Deep black and scattered sludge is formed at the bottom of underground water, and the fluorine removal rate in the liquid culture solution is measured to be 82.45%, which indicates that the biological agent is successfully prepared;
step three, preparing biological seed crystals:
mixing the biological agent obtained in the second step with the nutrient solution II in a proportion of 10% in a 250ml conical flask, sealing the conical flask by using a sealing film, and culturing at a vibration speed of 180 revolutions per minute on a constant temperature vibrator under an aerobic condition at a temperature of 30 ℃. After 36h of incubation, the solution was sonicated for 10 minutes. Taking out small particles of biological sediment generated on the culture substrate, separating with a centrifuge at 8000 rpm for 15min, repeatedly washing biological seed crystal with deionized water to remove soluble impurities, inactivating bacteria at this time, drying the sample at 60deg.C for 24 hr, sieving with 100 sieve to obtain powder, and finally forming biological seed crystal with bacteria as core.
The formula of the enriched nutrient solution II in the step three is as follows (in terms of mass concentration):
C 4 H 4 Na 2 O 4 ·6H 2 O：0.5g/L ，NaNO 3 ：0.10g/L，NaHCO 3 ：0.5g/L
KH 2 PO 4 ：0.05g/L，MgCl 2 ：0.05 g /L，CaCl 2 :0.5g/L and 0.0075-0.0125 g/L of trace elements.
Wherein the microelements comprise the following raw materials in percentage by mass:
EDTA：1.0g/L， ZnSO 4 ：0.5g/L， MnCl 2 ·4H 2 O：0.2g/L， MgSO 4 ·7H 2 O：0.5g/L，CuSO 4 ·5H 2 O：0.5g/L ， CoCl 2 ·6H 2 O：0.2g/L，FeSO 4 ·7H 2 o:0.5g/L, ph=7.0.
The method for synchronously removing calcium and fluorine in the underground water comprises the following steps of:
first, the process water flows into the mixing reactor. After charging, biological seed crystals are added into the reactor, the adding amount is 1.5/g/L, the reactor enters a treatment stage, the temperature is 25 ℃, and the rotating speed is 100r/min. And (3) standing for 20min after stirring is finished, discharging the supernatant after the treatment, and then re-carrying out water inflow of the second round. The reaction time was set to 4 hours, this example was supplemented with 2.49mg/L of fluorine to meet the initial fluorine concentration for optimal adsorption efficiency,
from fig. 6 and 7, the efficiency of removing fluorine and calcium in the initial operation period of the reactor is lower, the efficiency of removing fluorine and calcium in the reactor is gradually increased along with the extension of time, the fluorine removal rate of the reactor in the steady period can reach 86.00%, the calcium removal rate reaches 75.56%, and the better fluorine and calcium removal capability is shown.
The invention is not limited to the above embodiments, and based on the technical solution disclosed in the invention, a person skilled in the art may make some substitutions and modifications to some technical features thereof without creative effort according to the technical content disclosed, and all the substitutions and modifications are within the protection scope of the invention.
Claims (4)
1. A method for preparing biological seed crystals, which is characterized by comprising the following steps:
step one, enrichment culture of sludge: obtaining a mud-water mixture from underground water, adding a nutrient solution I into the mud-water mixture, carrying out enrichment culture on the mud-water mixture added with the nutrient solution I under a constant-temperature aerobic condition, and collecting enriched sludge;
the sludge enrichment culture comprises the following steps: firstly, adding 1-3mg/L sodium fluoride solution into a mud-water mixture obtained from underground water, standing, replacing half of supernatant as nutrient solution I, carrying out enrichment culture for 7-10 days, and oscillating 3-4 times per day by adopting a shaking table with the rotating speed of 30-60 rpm for 10-15 minutes each time; secondly, adding sodium fluoride solution with concentration 200% -600% higher than that of the first step, and partially replacing the nutrient solution I in the last step; third, repeating the second step until the fluorine removal rate in the liquid culture solution reaches more than 70%, and completing sludge enrichment;
step two, preparation of biological bacteria: adding a nutrient solution I into the collected enriched sludge, performing constant-temperature culture, and collecting a biological bacterial agent precipitate;
the preparation of the biological agent comprises the following steps: firstly, adding a nutrient solution I into enriched sludge, wherein the enriched sludge and the nutrient solution I are mixed according to the mass ratio of 1:100-150, and culturing at a constant temperature of 25-30 ℃; step two, replacing the liquid culture solution once every other period, wherein the liquid culture solution is nutrient solution I and sterilized underground water according to the volume ratio of 1: 1-3, wherein the concentration of the nutrient solution I of the liquid culture solution which is replaced successively is reduced in sequence; until the bottom of the underground water is deep black and is in a bulk sludge state, and the fluorine removal rate in the liquid culture solution is measured to be more than 70%, the preparation of the biological agent is completed;
step three, preparing biological seed crystals: the mass ratio of the microbial inoculum sediment to the nutrient solution II obtained in the step two is 1:7-20, culturing under constant-temperature aerobic condition, precipitating, separating, washing, drying, and sieving to obtain biological seed crystal;
the formula of the nutrient solution I is as follows:
C 4 H 4 Na 2 O 4 ·6H 2 O：0.8-1.2g/L ，NaNO 3 ：0.08-0.12g/L，NaHCO 3 ：0.8-1.2g/L，CaCl 2 :0.4-0.6g/L and 0.0075-0.0125 g/L of trace elements;
the formula of the nutrient solution II is as follows:
C 4 H 4 Na 2 O 4 ·6H 2 O：0.4-0.6g/L ，NaNO 3 ：0.08-0.12g/L，NaHCO 3 ：0.4-0.6g/L，KH 2 PO 4 ：0.04-0.06g/L，MgCl 2 ：0.04-0.06 g /L，CaCl 2 :0.4-0.6g/L and 0.0075-0.0125 g/L of trace elements.
2. The method for preparing biological seed crystals according to claim 1, wherein: the microelements comprise the following raw materials in percentage by mass:
EDTA：0.8-1.2g/L， ZnSO 4： 0.4-0.6g/L，MnCl 2 ·4H 2 O：0.1-0.3g/L ，MgSO 4 ·7H 2 O：0.4-0.6g/L，CuSO 4 ·5H 2 O：0.4-0.6g/L ，CoCl 2 ·6H 2 O：0.1-0.3g/L ，FeSO 4 ·7H 2 o:0.4-0.6g/L, ph=7.0.
3. The method for preparing biological seed crystals according to claim 1, wherein: in the first step, the mud-water mixture and the nutrient solution I are uniformly mixed according to the mass ratio of 2-4:1.
4. The method for preparing biological seed crystals according to claim 1, wherein: the preparation of the biological seed crystal specifically comprises the following steps: the microbial inoculum sediment and the nutrient solution II obtained in the second step are mixed according to the mass ratio of 1:7-20, culturing at a vibration speed of 160-180 r/min by a constant temperature oscillator under aerobic condition with a temperature of 30-35 ℃ for 24-36h, treating the mixed solution with ultrasonic waves for 8-15 min, taking out small biological precipitate particles generated on the culture substrate, separating with a centrifuge, repeatedly washing biological seed crystal with deionized water to remove soluble impurities, drying, sieving to form powder, and obtaining the biological seed crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011246138.1A CN112456654B (en) | 2020-11-10 | 2020-11-10 | Preparation method and application of biological seed crystal and method for synchronously removing calcium and fluorine in underground water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011246138.1A CN112456654B (en) | 2020-11-10 | 2020-11-10 | Preparation method and application of biological seed crystal and method for synchronously removing calcium and fluorine in underground water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112456654A CN112456654A (en) | 2021-03-09 |
| CN112456654B true CN112456654B (en) | 2024-01-30 |
Family
ID=74826040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011246138.1A Active CN112456654B (en) | 2020-11-10 | 2020-11-10 | Preparation method and application of biological seed crystal and method for synchronously removing calcium and fluorine in underground water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112456654B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113060841A (en) * | 2021-04-16 | 2021-07-02 | 北京涞澈科技发展有限公司 | Microbial material applied to high-concentration fluorine-containing wastewater treatment and preparation method thereof |
| CN113264592A (en) * | 2021-05-06 | 2021-08-17 | 北京涞澈科技发展有限公司 | Efficient defluorination microbial flocculant applied to photovoltaic wastewater |
| CN114262066A (en) * | 2021-12-23 | 2022-04-01 | 西安建筑科技大学 | Method and reactor for synchronously removing organic matters by microorganism-induced calcium precipitation |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203048649U (en) * | 2012-10-23 | 2013-07-10 | 上海问鼎环保科技有限公司 | Device for removing copper ions in chemical plating wastewater |
| CN107523560A (en) * | 2017-09-05 | 2017-12-29 | 西安建筑科技大学 | Nitrate nitrogen removal fixation support and preparation method in Low Concentration Iron ion underground water |
| CN109354238A (en) * | 2018-10-12 | 2019-02-19 | 天津大学 | The method and its processing unit of hardness in multistep combined removal water |
| CN110589991A (en) * | 2019-09-10 | 2019-12-20 | 同济大学 | Method for removing calcium ions in high-concentration organic wastewater |
| CN110776205A (en) * | 2019-11-18 | 2020-02-11 | 大连理工大学 | Device for simultaneously removing fluorine ions and nitrate nitrogen in graphite production wastewater |
| CN111792661A (en) * | 2020-07-29 | 2020-10-20 | 华南农业大学 | Submicron spherical biological calcium carbonate and preparation method and application thereof |
-
2020
- 2020-11-10 CN CN202011246138.1A patent/CN112456654B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203048649U (en) * | 2012-10-23 | 2013-07-10 | 上海问鼎环保科技有限公司 | Device for removing copper ions in chemical plating wastewater |
| CN107523560A (en) * | 2017-09-05 | 2017-12-29 | 西安建筑科技大学 | Nitrate nitrogen removal fixation support and preparation method in Low Concentration Iron ion underground water |
| CN109354238A (en) * | 2018-10-12 | 2019-02-19 | 天津大学 | The method and its processing unit of hardness in multistep combined removal water |
| CN110589991A (en) * | 2019-09-10 | 2019-12-20 | 同济大学 | Method for removing calcium ions in high-concentration organic wastewater |
| CN110776205A (en) * | 2019-11-18 | 2020-02-11 | 大连理工大学 | Device for simultaneously removing fluorine ions and nitrate nitrogen in graphite production wastewater |
| CN111792661A (en) * | 2020-07-29 | 2020-10-20 | 华南农业大学 | Submicron spherical biological calcium carbonate and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| "A new technology for simultaneous calcium –nitrate and fluoride removal in the biofilm reactor";Jun feng Su et al.;Journal of Hazardous Materials(第第399期期);第1-10页 * |
| Jun feng su et al.."The performance and mechanism of simultaneous removal of fluoride,calcium, and nitrate by calcium precipitating strain Acinetobacter sp. H12". Ecotoxicology and Environmental Safety.2019,(第 第187期期),第1-9页. * |
| 诱导结晶法去除地下水中氟离子;黄廷林;孙田;邓林煜;;环境工程学报;第8卷(第01期);第1-5页 * |
| 黄廷林 ; 孙田 ; 邓林煜 ; .诱导结晶法去除地下水中氟离子.环境工程学报.2014,第8卷(第01期),第1-5页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112456654A (en) | 2021-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112456654B (en) | Preparation method and application of biological seed crystal and method for synchronously removing calcium and fluorine in underground water | |
| Krishnamoorthy et al. | Engineering principles and process designs for phosphorus recovery as struvite: A comprehensive review | |
| CN107840544A (en) | Electroplating effluent treatment method | |
| CN101343090A (en) | Lanthanide series water treatment agent and method of preparing the same | |
| KR101462033B1 (en) | Sewage and wastewater treatment system with crystallization apparatus for phosphorus recovery | |
| CN107285501A (en) | A kind of copper-bearing industrial wastewater processing method | |
| CN203159389U (en) | Aquatic product processing wastewater treatment equipment | |
| CN104355488A (en) | Domestic sewage treatment method and domestic sewage treatment device | |
| CN113353903A (en) | Preparation method of hydroxyapatite and constructed wetland system constructed by same | |
| CN106417365B (en) | A kind of the chemical algae removing agent and its application method of eutrophic water algae | |
| CN103043860B (en) | Leachate utilizing equipment and method in biomass landfilling process | |
| KR100756282B1 (en) | Apparatus and method for algal bloom control | |
| CN204281502U (en) | Waste disposal plant | |
| CN106732469A (en) | A kind of preparation method of magnetic absorption dephosphorization agent and its renovation process of product | |
| CN107021580B (en) | Method for recycling waste liquid generated after extracting tigogenin from sisal hemp | |
| CN102765813A (en) | Method for treating industrial and domestic sewage by active organisms | |
| JP2010233551A (en) | Method for culturing microalga | |
| CN104003576A (en) | Eutrophic water body phycomycete symbiosis purification technique | |
| JP2015508331A (en) | Ammonia nitrogen removal from organic wastewater | |
| Perales-Pérez et al. | Process for nutrient recycling from intensive aquaculture through microalgae-bacteria consortium | |
| JP2946052B2 (en) | Method of obtaining drinking water from polluted water of rivers and lakes using Chlamydomonas single cell green algae | |
| CN205556387U (en) | Effluent treatment plant of former medicine preparation | |
| CN204824477U (en) | Remove device of high concentration phosphorus in waste water | |
| CN109650557A (en) | A kind of method, microorganism antisludging agent and purposes reducing Calcium in Seawater magnesium ion content | |
| CN204224389U (en) | Waste disposal plant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |