CN112456654A - 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
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- CN112456654A CN112456654A CN202011246138.1A CN202011246138A CN112456654A CN 112456654 A CN112456654 A CN 112456654A CN 202011246138 A CN202011246138 A CN 202011246138A CN 112456654 A CN112456654 A CN 112456654A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000011737 fluorine Substances 0.000 title claims abstract description 58
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 58
- 239000013078 crystal Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000011575 calcium Substances 0.000 title claims abstract description 39
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title claims abstract 9
- 239000000243 solution Substances 0.000 claims description 102
- 235000015097 nutrients Nutrition 0.000 claims description 62
- 238000002156 mixing Methods 0.000 claims description 34
- 239000010802 sludge Substances 0.000 claims description 29
- 238000009630 liquid culture Methods 0.000 claims description 28
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 24
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 24
- 239000011573 trace mineral Substances 0.000 claims description 20
- 235000013619 trace mineral Nutrition 0.000 claims description 20
- 239000003124 biologic agent Substances 0.000 claims description 19
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 18
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 14
- 239000001110 calcium chloride Substances 0.000 claims description 14
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 14
- 238000012258 culturing Methods 0.000 claims description 14
- 239000003673 groundwater Substances 0.000 claims description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 11
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 10
- 239000007836 KH2PO4 Substances 0.000 claims description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 9
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 9
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 8
- 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
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 8
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 8
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 8
- 229910052564 epsomite Inorganic materials 0.000 claims description 8
- 239000011565 manganese chloride Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 8
- 239000011686 zinc sulphate Substances 0.000 claims description 8
- 238000001035 drying Methods 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
- 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
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002068 microbial inoculum Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 abstract description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 15
- 238000001556 precipitation Methods 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 8
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 48
- 239000001963 growth medium Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 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
- 238000007789 sealing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 230000003203 everyday effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052603 melanterite Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 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
- 239000000758 substrate Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 101000965313 Legionella pneumophila subsp. pneumophila (strain Philadelphia 1 / ATCC 33152 / DSM 7513) Aconitate hydratase A Proteins 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
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 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
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 229910052587 fluorapatite Inorganic materials 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000004571 lime 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 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
- 210000004958 brain cell Anatomy 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
- 238000011109 contamination Methods 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
- 238000000909 electrodialysis Methods 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical class [H]O* 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 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
- 229940085991 phosphate ion Drugs 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
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 238000011105 stabilization Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000004936 stimulating effect Effects 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
Images
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
Abstract
The invention discloses a preparation method and application of biological seed crystals and a method for synchronously removing calcium and fluorine in underground water. The invention provides a method for synchronously removing fluorine and calcium pollutants in underground water by using biological crystal seeds taking 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 crystal seeds by bacteria, and the crystal seeds are taken out at the initial stage of nucleation to prepare the biological crystal seeds.
Description
Technical Field
The invention belongs to the technical field of underground water treatment, and particularly relates to a method for removing calcium and fluorine pollutants in underground water by using biological seed crystals.
Background
The growing problem of groundwater contamination has raised concern in many countries around the world where groundwater in parts of the country has the form F-、Ca2+The pollution problem affects the water quality of drinking water, thereby causing the limited development of social and economic and harming the health of people. Particularly in northern areas, the method belongs to a high-fluorine water disaster area.
Excessive fluoride uptake can lead to changes in tooth enamel, leading to staining and pitting. Fluoride can concentrate in bone, stimulating the growth of bone cells, altering the structure of various tissues and ultimately weakening the bone. More seriously, drinking water containing high concentrations of fluoride can have effects on brain and nerve cells, resulting in other adverse health effects, including damage to non-skeletal tissues such as the kidney, reproductive and digestive systems. In addition, fluorine pollution of underground water can also cause poisoning of animals and plants and influence the production of agriculture and animal husbandry. For industry and homes, excessive hardness in a body of water can cause scaling problems in equipment, pipes, tanks, etc. When urban citizens drink tap water, due to the existence of high hardness, a large amount of white scales can appear in water which originally meets drinking requirements after boiling, and a plurality of hazards such as discomfort in sense and the like exist.
The prior fluoride removal technology in underground water mainly comprises the following steps: electrodialysis, reverse osmosis, nanofiltration, adsorption, bioadsorption, nalgold technology, ion exchange. The above-mentioned removing processes have the advantages of no need of medium, high absorption capacity and easy obtaining of corresponding chemical products. However, the main disadvantages associated with these processes are high running costs, the generation of large amounts of waste such as water desalination, excessive hydraulic and electrical power consumption, and the disposal of the generated waste. These physicochemical methods are conversely ineffective or expensive when the fluoride ion contaminant concentration is very low. The common hardness removal techniques in groundwater mainly include: 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 is developed, reverse osmosis technology has become one of the main measures for groundwater softening. 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 strict requirements on operation conditions. 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. Biological seed material can promote crystallization and then precipitate with attached crystals, which can significantly shorten 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 groundwater by using biological crystal seeds taking 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 to realize:
a method for preparing biological seed crystals comprises 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;
step two, preparation of the biological agent: adding a nutrient solution I into the collected enriched sludge, carrying out constant-temperature culture, and collecting a biological agent precipitate;
step three, preparation of biological seed crystal: the biological agent obtained in the step two and the nutrient solution II 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:
C4H4Na2O4·6H2O：0.8-1.2g/L，NaNO3：0.08-0.12g/L，NaHCO3：0.8-1.2g/L，CaCl2: 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:
C4H4Na2O4·6H2O：0.4-0.6g/L，NaNO3：0.08-0.12g/L，NaHCO3：0.4-0.6g/L，KH2PO4：0.04-0.06g/L，MgCl2：0.04-0.06g/L，CaCl2: 0.4-0.6g/L and 0.0075-0.0125 g/L of trace elements.
The preferable formula of the nutrient solution I is as follows: c4H4Na2O4·6H2O：0.8-1.2g/L，NaNO3：0.08-0.12g/L，NaHCO3：0.8-1.2g/L，KH2PO4：0.04-0.06g/L，MgCl2：0.04-0.06g/L，CaCl2: 0.4-0.6g/L and 0.0075-0.0125 g/L of trace elements.
Further, the trace elements comprise the following raw materials in percentage by mass:
EDTA：0.8-1.2g/L，ZnSO4：0.4-0.6g/L，MnCl2·4H2O：0.1-0.3g/L，MgSO4·7H2O：0.4-0.6g/L，CuSO4·5H2O：0.4-0.6g/L，CoCl2·6H2O：0.1-0.3g/L，FeSO4·7H2o: 0.4-0.6g/L, pH 7.0.
Preferably, the muddy 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 as a nutrient solution I, carrying out enrichment culture for 7-10 days, and shaking for 3-4 times a day by adopting a shaking table with the rotating speed of 30-60 rpm, wherein each time lasts for 10-15 minutes; secondly, adding a sodium fluoride solution with the concentration 200-600% higher than that of the first step, and partially replacing the nutrient solution I in the previous step; and thirdly, repeating the content of the second step until the removal rate of fluorine in the liquid culture solution reaches more than 70 percent, and finishing sludge enrichment.
Further, the preparation of the biological agent comprises the following steps: step one, adding a nutrient solution I into the 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 ℃; and step two, replacing the liquid culture solution every other cycle, wherein the liquid culture solution is prepared by mixing nutrient solution I and sterilized underground water according to the volume ratio of 1: 1-3, and the concentration of the nutrient solution I of the liquid culture solution which is replaced successively is reduced in sequence; and (3) completing the preparation of the biological agent when the removal rate of fluorine in the liquid culture solution is determined to be more than 70% until the bottom of underground water becomes dark black and scattered sludge.
Further, the preparation of the biological seed crystal specifically comprises: and (3) mixing the microbial inoculum precipitate obtained in the step two with a nutrient solution II according to a mass ratio of 1: 7-20, culturing at 30-35 ℃ under aerobic condition with a constant temperature oscillator 160-180 rpm, culturing for 24-36h, treating the mixed solution with ultrasonic waves for 8-15 min, taking out small biological precipitate particles generated at the bottom of the culture part, separating by a centrifuge, repeatedly washing biological seed crystals with deionized water to remove soluble impurities, drying at 60 ℃ for 24 h, and sieving to form powder to obtain the biological seed crystals.
The biological seed crystal provided by the invention can be used for 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 is as follows: the treated water flows into a mixing reactor, and biological seed crystals prepared according to the method of claims 1-5 are added into the reactor, wherein the adding amount of the biological seed crystals is 1-2g/L, and the temperature is kept at 25 +/-2 ℃;
second, Ca when water is fed2+:F-When the mass concentration is more than 60-150, the mixing reaction time is 5-3 hours, and when the Ca of the inlet water is2+: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 needs to be supplemented to the bottom of the mixing reactor until the concentration of the calcium ions reaches 30 mg/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, the mixing reactor at least comprises a water inlet and a water outlet, and the biological seed crystal prepared by the method is filled in the container of the mixing reactor.
Preferably, a stirrer is also arranged in the mixing reactor, and the rotating speed of the stirrer is 100-150 r/min.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention induces the formation of biological seeds by bacteria, the seeds are taken out in the initial stage of nucleation (culturing for 36-48h) to prepare biological seeds, and then the seeds are added to the culture medium containing F-And Ca2+The fluorine and calcium ions in the water body are successfully removed through the adsorption effect and the crystallization nucleation effect in the polluted underground water.
(2) The invention utilizes the crystal induced crystallization synthesized by calcium carbonate precipitation (MICP) induced by microorganisms as a high-efficiency fluorine adsorbent, and provides a cleaner and more economic 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 yielding water is avoided.
(3) The biological seed crystal adopted by the invention for treating the underground water 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 underground water. Calcium fluorophosphate is formed in the process of removing fluorine, so the method also has the effect of removing phosphorus and calcium.
(4) The invention adopts biological crystal seed adsorption and induced precipitation, and compared with chemical precipitation using lime and calcium salt, the 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 the induced crystallization is performed on the seed material, and thus does not produce fine precipitates that are difficult to remove.
Drawings
FIG. 1 is a diagram of a biological seed formation reaction process in the present invention; wherein FIG. 1(a) is a biological agent cultured for 36 h; (b) before adding biological crystal seeds; (c) scanning electron microscope photo of the biological crystal after reaction.
FIG. 2 shows the results of fluorine removal in example 1 of the present invention.
FIG. 3 shows the results of calcium removal in example 1 of the present invention.
FIG. 4 shows the results of fluorine removal in example 2 of the present invention.
FIG. 5 shows the results of calcium removal in example 2 of the present invention.
FIG. 6 shows the results of fluorine removal in example 3 of the present invention.
FIG. 7 shows the results of calcium removal in example 3 of the present invention.
The invention is described in further detail below with reference to the drawings and the detailed description. The following description is of the preferred embodiment of the present invention only, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Detailed Description
The overall technical concept of the invention is based on the following technical mechanisms:
Cell+Ca2+＝Cell-Ca2+(Process of calcium precipitating bacteria attracting calcium ions)
Cell-Ca2++CO3 2-＝Cell-CaCO3(Process for calcium precipitation of calcium carbonate induced by calcium-precipitating bacteria)
CaCO3+2F-+H+＝CaF2+HCO3 -(ion exchange Process of calcium carbonate with fluoride ion adsorbed on the surface thereof)
Ca5(PO4)3OH+F-＝Ca5(PO4)3F+OH-(substitution of hydroxyl group with fluorine ion)
Ca2++2F-→CaF2(precipitation of free calcium and fluoride ions)
5Ca2++F-+3PO4 3-→Ca5(PO4)3F (calcium ion,Coprecipitation process of phosphate ion and fluoride ion)
Through the reaction, the fluorine and the calcium in the groundwater are removed simultaneously.
Example 1
Following the overall technical concept of the present invention, the groundwater to be treated in example 1 is groundwater from a certain farmer in a village in Changan region, xi province, and comprises the following steps:
step one, enrichment culture of sludge:
taking 10L of muddy water from a reservoir or a sewage plant as a bacteria source, taking the nutrient solution I as an acclimatization culture medium, and mixing the nutrient solution I with the water according to a mass ratio of 3: 1, placing the mixture into a 200ml conical flask, and carrying out enrichment culture in a constant-temperature incubator (at the temperature of 27 ℃) under aerobic conditions. Taking 7 days as a culture period in the enrichment culture process, adding sodium fluoride (fluorine concentration is 1, 3 and 5mg/L) with different concentrations into a conical flask in each period, standing, and replacing half of supernatant to obtain nutrient solution I; in the enrichment process, a shaking table with the rotating speed of 40 turns is adopted, shaking is carried out for 3 times every day, and each shaking time is 15 minutes, so that nutrient substances capable of providing bacteria growth are ensured in the reactor. After 3 weeks of enrichment in each enrichment cycle, the removal rate of fluorine is determined to be 75.95%, which indicates that the enrichment and domestication are completed;
the formula of the enriched nutrient solution I in the step I is as follows:
the nutrient solution I (nutrient solution for screening calcium-precipitating bacteria) is prepared by the following components in percentage by mass:
C4H4Na2O4·6H2O：0.8g/L，NaNO3：0.08g/L，NaHCO3：0.8g/L
CaCl2: 0.4g/L, 0.0075-0.0125 g/L of trace elements
Wherein the trace elements comprise the following raw materials in percentage by mass: EDTA: 0.8g/L, ZnSO4：0.4g/L，MnCl2·4H2O：0.1g/L，MgSO4·7H2O：0.4g/L，CuSO4·5H2O：0.4g/L，CoCl2·6H2O：0.1g/L，FeSO4·7H2O: 0.4g/L, pH 7.0.
Step two, preparation of the biological agent:
collecting the enriched sludge in the enriched conical flask, adding a nutrient solution I into the enriched sludge, and mixing the nutrient solution I with the mixed solution I in a ratio of 1: 150 in a volume ratio of 1 to 1, placing the conical flask into a constant-temperature shaking incubator to be cultured for 3 days at 27 ℃, and then replacing liquid culture solution every 3 days, wherein the liquid culture solution is prepared by mixing culture solution I and sterilized underground water according to a volume ratio of 1: 1-3, the replacement sequence is as follows: the nutrient solution I and the sterilized underground water are mixed from 1: the liquid culture medium, the nutrient solution I and the sterilized underground water which are composed of 1 part by weight: 2, the ratio of the liquid culture medium, the nutrient solution I and the sterilized underground water is 1: 3 proportion of liquid culture medium. Forming deep black and scattered sludge at the bottom of underground water, and determining that the fluorine removal rate in the liquid culture solution is 78.65 percent, which indicates that the biological agent is successfully prepared;
step three, preparation of biological seed crystal:
and (3) mixing the biological agent obtained in the step (II) 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 then culturing on a constant-temperature oscillator at a vibration speed of 180 revolutions per minute under an aerobic condition at the temperature of 30 ℃. After 36h incubation, the solution was sonicated for 10 minutes. Separating the small biological precipitate particles generated at the culture substrate part with a centrifuge at 8000 rpm for 15min, repeatedly washing the biological seed crystal with deionized water to remove soluble impurities, wherein the bacteria are inactivated, drying the sample at 60 deg.C for 24 hr, sieving with 100 mesh sieve to obtain powder, and finally forming the biological seed crystal.
The formula of the enriched nutrient solution II in the third step is as follows (by mass concentration):
C4H4Na2O4·6H2O：0.4g/L，NaNO3：0.08g/L，NaHCO3：0.4g/L
KH2PO4：0.04g/L，MgCl2：0.04g/L，CaCl2: 0.4g/L and 0.0075-0.0125 g/L of trace elements.
Wherein the trace elements comprise the following raw materials in percentage by mass:
EDTA：0.8g/L，ZnSO4：0.4g/L，MnCl2·4H2O：0.1g/L，MgSO4·7H2O：0.4g/L，CuSO4·5H2O：0.4g/L，CoCl2·6H2O：0.1g/L，FeSO4·7H2o: 0.4g/L, pH 7.0.
Further, the method for synchronously removing calcium and fluorine in underground water comprises the following steps:
first, the treated water flows into the mixing reactor. After liquid filling, adding biological seed crystal into the reactor, wherein the adding amount is 1g/L, and entering a treatment stage, the temperature is 25 ℃, and the rotating speed is 100 r/min. And (5) standing and settling for 20min after stirring is finished, discharging the treated supernatant, and then carrying out the second round of water inlet again. 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 optimum adsorption efficiency.
As can be seen from the graphs in FIGS. 2 and 3, the fluorine and calcium removal efficiency of the reactor is low at the initial stage of the operation of the reactor, the fluorine and calcium removal efficiency of the reactor is gradually increased along with the prolonging of the time, the fluorine removal rate of the reactor at the stable period can reach 83.06 percent, the calcium removal rate reaches 75.85 percent, and the good fluorine and calcium removal capability is shown.
Example 2
Following the overall technical concept of the present invention, the groundwater to be treated in example 2 is self-used groundwater from a certain village of Yi district, xi' an city, shaxi province, and comprises the following steps:
step one, enrichment culture of sludge:
taking 10L of muddy water from a reservoir or a sewage plant as a bacteria source, taking the nutrient solution I as an acclimatization culture medium, and mixing the nutrient solution I with the water according to a mass ratio of 3: 1, placing the mixture into a 200ml conical flask, and carrying out enrichment culture in a constant-temperature incubator (at the temperature of 27 ℃) under aerobic conditions. Taking 7 days as a culture period in the enrichment culture process, adding sodium fluoride (fluorine concentration is 1, 2 and 4mg/L) with different concentrations into a conical flask in each period, standing, and replacing half of supernatant 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 for 3 times every day, and each shaking time is 15 minutes, so that nutrient substances capable of providing bacteria growth are ensured in the reactor. After 3 weeks of enrichment in each enrichment cycle, the removal rate of fluorine was determined to be 78.45%, indicating that acclimation of the enriched sludge was completed.
The formula of the enriched nutrient solution I in the step I is as follows:
the nutrient solution I (nutrient solution for screening calcium-precipitating bacteria) is prepared by the following components in percentage by mass:
C4H4Na2O4·6H2O：1.2g/L，NaNO3：0.12g/L，NaHCO3：1.2g/L
KH2PO4：0.06g/L，MgCl2：0.06g/L，CaCl2: 0.6g/L and 0.0075-0.0125 g/L of trace elements;
wherein the trace elements comprise the following raw materials in percentage by mass: : EDTA: 1.2g/L, ZnSO4：0.6g/L，MnCl2·4H2O：0.3g/L，MgSO4·7H2O：0.6g/L，CuSO4·5H2O：0.6g/L，CoCl2·6H2O：0.3g/L，FeSO4·7H2O: 0.6g/L, pH 7.0.
Step two, preparation of the biological agent:
collecting the enriched sludge in the enriched conical flask, adding a culture solution I into the enriched sludge, and mixing the culture solution I with the weight ratio of 1:100 in a volume ratio of 1 to 100, placing the conical flask into a constant-temperature shaking incubator, culturing for 3 days at 27 ℃, and then replacing liquid culture solution every 3 days, wherein the liquid culture solution is prepared by mixing culture solution I and sterilized underground water according to a volume ratio of 1: 1-3, the replacement sequence is as follows: the culture solution I and the sterilized underground water are mixed from 1: the liquid culture medium, the culture solution I and the sterilized underground water which are composed of 1 part by weight: the liquid culture medium, the culture solution I and the sterilized underground water which are composed of 1.5 parts by weight are as follows: 2.5 proportion of the liquid culture medium. Forming deep black and scattered sludge at the bottom of underground water, and determining that the fluorine removal rate in the liquid culture solution is 79.55 percent, which indicates that the preparation of the biological agent is successful;
step three, preparation of biological seed crystal:
and (3) mixing the biological agent obtained in the step (II) 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 then culturing on a constant-temperature oscillator at a vibration speed of 180 revolutions per minute under an aerobic condition at the temperature of 30 ℃. After 36h incubation, the solution was sonicated for 10 minutes. Separating the small biological precipitate particles generated at the culture substrate part for 15min at 8000 rpm by using a centrifuge, repeatedly washing the biological seed crystal with deionized water to remove soluble impurities, wherein the bacteria are inactivated, drying the sample at 60 ℃ for 24 h, and sieving the sample with a 100-mesh sieve to form powder, thereby finally forming the biological seed crystal taking the bacteria as a core.
The formula of the enriched nutrient solution II in the third step is as follows (by mass concentration):
C4H4Na2O4·6H2O：0.6g/L，NaNO3：0.12g/L，NaHCO3：0.6g/L KH2PO4：0.06g/L，MgCl2：0.06g/L，CaCl2: 0.6g/L and 0.0075-0.0125 g/L of trace elements.
Wherein the trace elements comprise the following raw materials in percentage by mass: : EDTA: 1.2g/L, ZnSO4：0.6g/L，MnCl2·4H2O：0.3g/L，MgSO4·7H2O：0.6g/L，CuSO4·5H2O：0.6g/L，CoCl2·6H2O：0.3g/L，FeSO4·7H2O: 0.6g/L, pH 7.0.
The method for synchronously removing calcium and fluorine in underground water, which is provided by the invention, comprises the following specific steps:
first, the treated water flows into the mixing reactor. After liquid filling, adding biological seed crystal into the reactor, wherein the adding amount is 1.5g/L, and entering a treatment stage, the temperature is 25 ℃, and the rotating speed is 100 r/min. And (5) standing and settling for 20min after stirring is finished, discharging the treated supernatant, and then carrying out the second round of water inlet again. The reaction time was set to 4 hours. To the initial fluorine concentration supplemented with 2.69mg/L of fluorine to satisfy the optimum adsorption efficiency, this example was supplemented with 2.69mg/L of fluorine to satisfy the initial fluorine concentration of the optimum adsorption efficiency.
As can be seen from the graphs in FIGS. 4 and 5, the fluorine and calcium removal efficiency of the reactor is low at the initial stage of the operation of the reactor, the fluorine and calcium removal efficiency of the reactor is gradually increased along with the prolonging of the time, the fluorine removal rate of the reactor can reach 82.96% in the stable period of the reactor, the calcium removal rate reaches 74.45%, and the good fluorine and calcium removal capability is shown.
Example 3
Following the overall technical concept of the present invention, the groundwater to be treated in example 3 is self-used groundwater from a certain village in Changan district, xi' an city, Shaanxi province, and comprises the following steps:
step one, enrichment culture of sludge:
taking 10L of muddy water from a reservoir or a sewage plant as a bacteria source, taking the nutrient solution I as an acclimatization culture medium, and mixing the nutrient solution I with the water according to a mass ratio of 3: 1, placing the mixture into a 200ml conical flask, and carrying out enrichment culture in a constant-temperature incubator (at the temperature of 27 ℃) under aerobic conditions. Taking 7 days as a culture period in the enrichment culture process, adding sodium fluoride (fluorine concentration is 1, 2.5 and 3.5mg/L) with different concentrations into a conical flask in each period, standing, and replacing half of supernatant 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 for 3 times every day, and each shaking time is 15 minutes, so that nutrient substances capable of providing bacteria growth are ensured in the reactor. After 3 weeks of enrichment in each enrichment cycle, the removal rate of fluorine is determined to be 78.88%, which indicates that the enrichment and domestication are completed;
the formula of the enriched nutrient solution I in the step I is as follows:
the nutrient solution I (nutrient solution for screening calcium-precipitating bacteria) is prepared by the following components in percentage by mass:
C4H4Na2O4·6H2O：1.0g/L，NaNO3：0.1g/L，NaHCO3：1.0g/L
KH2PO4：0.04g/L，MgCl2：0.04g/L，CaCl2: 0.5g/L and 0.0075-0.0125 g/L of trace elements;
wherein the trace elements comprise the following raw materials in percentage by mass:
EDTA：1.0g/L，ZnSO4：0.5g/L，MnCl2·4H2O：0.2g/L，MgSO4·7H2O：0.5g/L，CuSO4·5H2O：0.5g/L，CoCl2·6H2O：0.2g/L，FeSO4·7H2o: 0.5g/L, pH 7.0.
Step two, preparation of the biological agent:
and collecting the enriched sludge in the enriched conical flask. Adding a culture solution I into the enriched sludge, and mixing the culture solution I with the culture solution I in a ratio of 1:100 in a volume ratio of 1 to 100, placing the conical flask into a constant-temperature shaking incubator, culturing for 3 days at 27 ℃, and then replacing liquid culture solution every 3 days, wherein the liquid culture solution is prepared by mixing culture solution I and sterilized underground water according to a volume ratio of 1: 1-3, the replacement sequence is as follows: the culture solution I and the sterilized underground water are mixed from 1: the liquid culture medium, the culture solution I and the sterilized underground water which are composed of 1 part by weight: the liquid culture medium, the culture solution I and the sterilized underground water which are composed of 1.5 parts by weight are as follows: 3 proportion of liquid culture medium. Forming deep black and scattered sludge at the bottom of underground water, and determining that the fluorine removal rate in the liquid culture solution is 82.45 percent, which indicates that the biological agent is successfully prepared;
step three, preparation of biological seed crystal:
and (3) mixing the biological agent obtained in the step (II) 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 then culturing on a constant-temperature oscillator at a vibration speed of 180 revolutions per minute under an aerobic condition at the temperature of 30 ℃. After 36h incubation, the solution was sonicated for 10 minutes. Separating the small biological precipitate particles generated at the culture substrate part for 15min at 8000 rpm by using a centrifuge, repeatedly washing the biological seed crystal with deionized water to remove soluble impurities, wherein the bacteria are inactivated, drying the sample at 60 ℃ for 24 h, and sieving the sample with a 100-mesh sieve to form powder, thereby finally forming the biological seed crystal taking the bacteria as a core.
The formula of the enriched nutrient solution II in the third step is as follows (by mass concentration):
C4H4Na2O4·6H2O：0.5g/L，NaNO3：0.10g/L，NaHCO3：0.5g/L KH2PO4：0.05g/L，MgCl2：0.05g/L，CaCl2: 0.5g/L and 0.0075-0.0125 g/L of trace elements.
Wherein the trace elements comprise the following raw materials in percentage by mass:
EDTA：1.0g/L，ZnSO4：0.5g/L，MnCl2·4H2O：0.2g/L，MgSO4·7H2O：0.5g/L，CuSO4·5H2O：0.5g/L，CoCl2·6H2O：0.2g/L，FeSO4·7H2o: 0.5g/L, pH 7.0.
The method for synchronously removing calcium and fluorine in underground water, which is provided by the invention, comprises the following steps:
first, the treated water flows into the mixing reactor. After liquid filling, adding biological seed crystal into the reactor, wherein the adding amount is 1.5g/L, and entering a treatment stage, the temperature is 25 ℃, and the rotating speed is 100 r/min. And (5) standing and settling for 20min after stirring is finished, discharging the treated supernatant, and then carrying out the second round of water inlet again. The reaction time was set to 4 hours, and this example was supplemented with 2.49mg/L of fluorine, to satisfy the initial fluorine concentration for optimum adsorption efficiency,
as can be seen from FIGS. 6 and 7, the fluorine and calcium removal efficiency of the reactor is low at the initial stage of operation of the reactor, and gradually increases with the time, the fluorine removal rate of the reactor can reach 86.00% in the stabilization period of the reactor, the calcium removal rate reaches 75.56%, and the good fluorine and calcium removal capability is shown.
The present invention is not limited to the above-mentioned embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts according to the disclosed technical contents, and these substitutions and modifications are all within the protection scope of the present invention.
Claims (11)
1. A preparation method of biological seed crystals 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;
step two, preparation of the biological agent: adding a nutrient solution I into the collected enriched sludge, carrying out constant-temperature culture, and collecting a biological agent precipitate;
step three, preparation of biological seed crystal: and (3) mixing the microbial inoculum precipitate obtained in the step two with a nutrient solution II according to a 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:
C4H4Na2O4·6H2O：0.8-1.2g/L，NaNO3：0.08-0.12g/L，NaHCO3：0.8-1.2g/L，CaCl2: 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:
C4H4Na2O4·6H2O：0.4-0.6g/L，NaNO3：0.08-0.12g/L，NaHCO3：0.4-0.6g/L，KH2PO4：0.04-0.06g/L，MgCl2：0.04-0.06g/L，CaCl2: 0.4-0.6g/L and 0.0075-0.0125 g/L of trace elements.
2. A method of preparing biological seeds according to claim 1, wherein: the preferable formula of the nutrient solution I is as follows: c4H4Na2O4·6H2O：0.8-1.2g/L，NaNO3：0.08-0.12g/L，NaHCO3：0.8-1.2g/L，KH2PO4：0.04-0.06g/L，MgCl2：0.04-0.06g/L，CaCl2: 0.4-0.6g/L and 0.0075-0.0125 g/L of trace elements.
3. A method of preparing biological seed crystals according to claim 1 or 2, wherein: the trace elements comprise the following raw materials in percentage by mass:
EDTA：0.8-1.2g/L，ZnSO4：0.4-0.6g/L，MnCl2·4H2O：0.1-0.3g/L，MgSO4·7H2O：0.4-0.6g/L，CuSO4·5H2O：0.4-0.6g/L，CoCl2·6H2O：0.1-0.3g/L，FeSO4·7H2o: 0.4-0.6g/L, pH 7.0.
4. A method of preparing biological seeds according to claim 1, wherein: in the first step, the muddy water mixture and the nutrient solution I are uniformly mixed according to the mass ratio of 2-4: 1.
5. A method of preparing a biological seed crystal according to any one of claims 3 to 4, characterized in that: the sludge enrichment culture comprises the following steps: adding 1-3mg/L sodium fluoride solution into a mud-water mixture obtained from underground water, standing, replacing half of the supernatant to be a nutrient solution I, carrying out enrichment culture for 7-10 days, shaking for 3-4 times a day by adopting a shaking table with the rotating speed of 30-60 rpm, and each time for 10-15 minutes; secondly, adding a sodium fluoride solution with the concentration 200-600% higher than that of the first step, and partially replacing the nutrient solution I in the previous step; and thirdly, repeating the second step until the removal rate of fluorine in the liquid culture solution reaches more than 70%, and finishing sludge enrichment.
6. A method of preparing biological seed crystals according to claim 5, wherein: the preparation of the biological agent comprises the following steps: step one, adding a nutrient solution I into the 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 ℃; and step two, replacing the liquid culture solution every other cycle, wherein the liquid culture solution is prepared by mixing nutrient solution I and sterilized underground water according to the volume ratio of 1: 1-3, and the concentration of the nutrient solution I of the liquid culture solution which is replaced successively is reduced in sequence; and (3) completing the preparation of the biological agent when the removal rate of fluorine in the liquid culture solution is determined to be more than 70% until the bottom of underground water becomes dark black and scattered sludge.
7. A method of preparing biological seed crystals according to claim 5, wherein: the preparation of the biological seed crystal specifically comprises the following steps: and (3) mixing the microbial inoculum precipitate obtained in the step two with a nutrient solution II according to a mass ratio of 1: 7-20, culturing at 30-35 ℃ under aerobic condition with a constant temperature oscillator 160-180 rpm, culturing for 24-36h, treating the mixed solution with ultrasonic waves for 8-15 min, taking out small biological precipitate particles generated at the bottom of the culture part, separating by a centrifuge, repeatedly washing biological seed crystals with deionized water to remove soluble impurities, drying, and sieving to form powder to obtain the biological seed crystals.
8. A method of preparing a biological seed according to claims 1 to 7, wherein: the biological seed crystal is used for synchronously removing calcium and fluorine in underground water.
9. A method for synchronously removing calcium and fluorine in underground water is characterized by comprising the following steps: the method comprises the following steps:
the first step is as follows: the treated water flows into a mixing reactor, and biological seed crystals prepared according to the method of claims 1-5 are added into the reactor, wherein the adding amount of the biological seed crystals is 1-2g/L, and the temperature is kept at 25 +/-2 ℃;
second, Ca when water is fed2+:F-When the mass concentration is more than 60-150, the mixing reaction time is 5-3 hours, and when the Ca of the inlet water is2+: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 needs to be supplemented to the bottom of the mixing reactor until the concentration of the calcium ions reaches 30 mg/L.
10. A mixed reactor for synchronously removing calcium and fluorine in underground water at least comprises a water inlet and a water outlet, and is characterized in that: the biological seed crystal prepared according to the method of claims 1 to 7 is added into the mixing reactor vessel.
11. A hybrid reactor for the simultaneous removal of calcium and fluorine from groundwater as claimed in claim 10, wherein: a stirrer is also arranged in the mixing reactor, and the rotating speed of the stirrer is 100-.
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