CN114807241A - Biogenic mineral for treating heavy metal wastewater in rare earth mining area and preparation method thereof - Google Patents
Biogenic mineral for treating heavy metal wastewater in rare earth mining area and preparation method thereof Download PDFInfo
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- 230000000035 biogenic effect Effects 0.000 title claims abstract description 56
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 56
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 28
- 239000011707 mineral Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 20
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 20
- 238000005065 mining Methods 0.000 title claims abstract description 16
- 239000002351 wastewater Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 18
- 241000194108 Bacillus licheniformis Species 0.000 claims abstract description 14
- 239000001963 growth medium Substances 0.000 claims abstract description 8
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 7
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 238000009630 liquid culture Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 11
- 244000005700 microbiome Species 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000002609 medium Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000001888 Peptone Substances 0.000 claims description 2
- 108010080698 Peptones Proteins 0.000 claims description 2
- 235000015278 beef Nutrition 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 235000019319 peptone Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 116
- 229910052567 struvite Inorganic materials 0.000 abstract description 85
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 abstract description 83
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002689 soil Substances 0.000 abstract description 4
- 238000005067 remediation Methods 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000009629 microbiological culture Methods 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 18
- 239000003463 adsorbent Substances 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 239000010865 sewage Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 238000012258 culturing Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
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- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229940041514 candida albicans extract Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000012137 tryptone Substances 0.000 description 2
- 239000012138 yeast extract Substances 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000006137 Luria-Bertani broth Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
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- 238000000227 grinding Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012533 medium component Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a biogenic mineral for treating heavy metal wastewater in a rare earth mining area and a preparation method thereof. The biogenic mineral is obtained by inoculating bacillus licheniformis LRL007 in a liquid culture medium containing soluble magnesium salt for culture; the Bacillus licheniformis LRL007 is separated from the Gannan rare earth ore field storage soil and is preserved in the China general microbiological culture Collection center (CGMCC) with the preservation number of CGMCC No.24275 in 1 month and 10 days of 2022. The preparation method is economic and environment-friendly, is simple and quick to operate, has low cost, and does not add any toxic and harmful substances in the synthesis process, so that secondary pollution is avoided; the obtained struvite is good in stability, has a well-developed porous structure, has excellent adsorption performance on single heavy metal and composite heavy metal polluted rare earth mining area wastewater, is wide in pH application range, and has a good application prospect on remediation of heavy metals in rare earth mining areas.
Description
Technical Field
The invention belongs to the technical field of environmental management, and particularly relates to a biogenic mineral for treating heavy metal wastewater in a rare earth mining area and a preparation method thereof.
Background
The application of the ammonium sulfate as the mineral leaching agent in the Gannan ionic rare earth mining process and the leakage of the associated heavy metal in the rare earth mining area can cause the compound pollution of ammonia nitrogen and heavy metal in the surface water body of the mining area, wherein the heavy metal pollution is mainly cadmium and copper which are the most common. When rare earth tail water is treated, only ammonia nitrogen is usually considered to be removed, and heavy metal ions are easily ignored to be removed.
The adsorption method is a simple and feasible method for treating the wastewater containing the heavy metal ions, has simple adsorption process, easy operation and practicability, and is widely applied to the aspect of wastewater treatment. The key of the technology is the adsorption material, the existing adsorption material is very limited in selection, and meanwhile, the adsorption capacity is low, the adsorption specificity is strong, the adsorption is greatly influenced by environmental factors such as pH, temperature and time, and the removal effect is not ideal in practical application. With the aggravation of heavy metal pollution in China and the stricter of the discharge standard of the rare earth tailings sewage, the invention of the novel adsorption material capable of removing the heavy metal in the sewage has positive significance for the ecological restoration of the rare earth mining area. Struvite, alsoWeighing magnesium ammonium phosphate (MgNH) 4 PO 4 ·6H 2 O), ammonia nitrogen in the sewage can be effectively removed through a struvite crystallization process, however, the struvite crystallization method has high requirement on the concentration of ammonia nitrogen in the sewage, has poor precipitation effect and is not suitable for removing tail water containing low-concentration ammonia nitrogen, and in addition, few people pay attention to the influence of the obtained struvite on the heavy metal removal effect and the environmental benefit.
Compared with struvite crystallization method, struvite microorganism induced mineralization method has unique advantages, and microorganisms metabolize nitrogen-containing and phosphorus-containing organic matters in sewage, so that organic nitrogen can be converted into inorganic Nitrogen (NH) 4 + ) The pH value of a mineralization system is increased, the mineralization removal of low-concentration ammonia nitrogen is realized, and organic phosphorus can be converted into inorganic Phosphorus (PO) 4 3- ) The method promotes the synthesis of struvite and avoids the limitation that the struvite inorganic precipitation process can only remove and recover inorganic nitrogen and phosphorus. Many microorganisms in the environment can induce the formation of struvite, and the struvite synthesized by the microorganisms is generally called biogenic struvite, and in fact, more or less microorganisms are involved in the process of treating ammonia nitrogen sewage through the crystallization of the struvite. At present, the preparation method of chemically synthesized struvite and the adsorption of the struvite to heavy metals are researched, but the low-cost preparation method of biological struvite and the research on the adsorption effect of the biological struvite to the heavy metals are not basically researched, particularly, the research on the remediation of a water body polluted by composite heavy metals is not paid enough attention, and the development and the application of the biological struvite in the field of the remediation of the heavy metals are greatly limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a biogenic mineral for treating heavy metal wastewater in a rare earth mining area and a preparation method thereof, and specifically adopts the following technical scheme:
a preparation method of biogenic minerals for treating heavy metal wastewater in a rare earth mining area comprises the following steps: inoculating bacillus licheniformis LRL007 into a liquid culture medium containing soluble magnesium salt for culture to obtain the biogenic mineral (namely biogenic struvite); the bacillus licheniformis LRL007 is separated from soil in a Gannan rare earth ore region yard (24 degrees 59 'N, 115 degrees 02' E), is preserved in the common microorganism center of China Committee for culture Collection of microorganisms at 1 month and 10 days in 2022, has the preservation address of No. 3 Hospital No. 1 of North Chen West Lu of the sunward region in Beijing, and has the preservation number of CGMCC No. 24275. The bacillus licheniformis LRL007 adopted in the method can also generate a large amount of alkaline substances in the culture process, so that the pH value in the solution can be obviously improved, the formation of struvite is promoted, an additional alkali source is not required to be added like the traditional method, and the cost of struvite mineralization is effectively reduced.
Preferably, the liquid culture medium is an LB culture medium or a beef extract peptone culture medium; the addition amount of the soluble magnesium salt is 0.5-1 g/L. When the struvite is prepared by the traditional method, the addition amount of the magnesium source is generally 3-8 g/L, but the method only needs to add 0.5-1 g/L, so that the cost is greatly reduced.
Preferably, the inoculation process of the bacillus licheniformis LRL007 is as follows: adding 2-5 mL of seed liquid (without additionally adding an alkali source) into every 1000mL of culture medium, wherein the concentration of the Bacillus licheniformis LRL007 in the seed liquid is (8-38) multiplied by 10 7 cfu/mL。
Preferably, the temperature in the culture process is 30-37 ℃, and the time is 72-168 hours; and after the culture is finished, drying the precipitate to obtain the biogenic mineral.
Preferably, the soluble magnesium salt is magnesium chloride.
The biogenic mineral prepared by the preparation method has porous surface, is mostly irregular, can also form spherical porous laminated characteristic aggregates, has the surface mainly with negative charge when the pH is 5.0, has Zeta potential of-17.53 +/-1.01 mV, and can promote the adsorption of heavy metal ions. The mineral composition of the biogenic mineral is as follows according to the percentage content of element oxide: p 2 O 5 47.76％、MgO 43.45％、CaO 2.34％、Na 2 O 1.22％、SiO 2 0.46％、K 2 O0.26% and others 4.51%.
The biogenic mineral can be used for treating heavy metal polluted wastewater, particularly heavy metal polluted wastewater in a rare earth mining area; the maximum adsorption capacity of Cd (II) and Cu (II) can reach 357.14 and 344.83mg/g respectively, and the method also has good effect on restoring water bodies which are subjected to Cd (II) and Cu (II) composite pollution. In addition, the biogenic struvite has good buffering capacity to an acid environment, can still keep good stability and heavy metal adsorption characteristics under the environment that the pH value is more than or equal to 3.0, has the optimal adsorbent amount of 2.5g/L, can reach balance after being adsorbed for 1 hour, and can obviously improve the adsorption efficiency after the temperature rises.
The invention has the beneficial effects that:
(1) the biogenic struvite has excellent adsorption performance on heavy metals, and the maximum adsorption capacity of the biogenic struvite on the heavy metals Cd (II) and Cu (II) can reach 357.14 and 344.83mg/g respectively; meanwhile, the method has better effect on the restoration of Cd (II) and Cu (II) composite polluted water bodies.
(2) The biogenic struvite has wide pH application range, is relatively stable (acid-resistant) especially in an acid environment, has good buffering capacity, and can still keep good heavy metal adsorption property in an environment with the pH value more than or equal to 3; the adsorption of heavy metal is fast under an acid environment (pH is 5.0), the adsorption balance can be achieved after 60 minutes of adsorption, the adsorption kinetic process conforms to a pseudo-second-order kinetic model, and the adsorption process is dominated by chemical adsorption; the adsorption process of the heavy metal is an endothermic reaction process, the adsorption capacity can be continuously increased along with the rise of the temperature, and the increase of the temperature is beneficial to the adsorption of the heavy metal ions.
(3) The preparation method of the biological source struvite is economic and environment-friendly, simple and rapid to operate, low in cost, good in stability of the obtained struvite and good in development of a porous structure; no toxic and harmful substances are added in the synthesis process, so that the biological source struvite product does not bring secondary pollution, has no potential risk to the environment, and has good application prospect for repairing heavy metals.
Drawings
FIG. 1 is a graph showing the structural and morphological features of the biogenic struvite in example 1; a is an XRD spectrum, b is an FTIR spectrum, c is a TG-DTG result image, and d is an SEM result image;
FIG. 2 is a graph showing the results of example 2 showing the effect of different adsorbent amounts on the adsorption performance of biogenic struvite; a is an adsorption efficiency influence result graph, and b is an adsorption quantity influence result graph;
FIG. 3 is a graph showing the results of different pH effects on the adsorption performance of biogenic struvite;
FIG. 4 is a graph showing the effect of different times on the adsorption performance of biogenic struvite and the results of its adsorption kinetics; a is a graph of the change condition of the adsorption efficiency along with the adsorption time, and b is a graph of the fitting result of a pseudo first-order kinetic model; c is a pseudo-second-order dynamics model fitting result graph;
FIG. 5 is a graph showing the results of different temperatures affecting the performance characteristics of biogenic struvite.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments and the accompanying drawings to fully understand the objects, aspects and effects of the present invention.
Example 1:
the preparation method of the biological source struvite comprises the following steps:
preparation of strain liquid: in 200mL of sterilized LB liquid medium [ (tryptone 1% (m/V), yeast extract 0.5% (m/V), NaCl 1% (m/V), pH 6.5 ≤ 7.5]Inoculating 1-2 ring Bacillus licheniformis (CGMCC No.24275), and shake culturing in a shaker at 30 deg.C and 180rpm for about 10 hr to prepare strain liquid with effective viable count [ 3.85 + -0.49) x 10 8 cfu/mL ]. Wherein, the Bacillus licheniformis LRL007 is a strain separated from soil of rare earth mineral storage yard (24 degrees 59 'N, 115 degrees 02' E) in Gannan.
Amplification culture and induction synthesis of biological source struvite: a clean 250mL Erlenmeyer flask was charged with 100mL of MgCl-containing solution 2 (0.8g) of LB liquid medium. Sterilizing at 115 deg.C for 30min, inoculating 2mL strain liquid, setting 40 parallel strains, and shake culturing at 30 deg.C and 180rpm for 7 days to induce formation of biogenic struvite.
Collecting the biological source guano stone: centrifuging the fermentation liquor at 8000rpm for 10 min; and drying the collected precipitate in an oven at 55 ℃, grinding, and sieving with a 100-mesh sieve for later use.
And fourthly, analyzing the structure and the morphology of the precipitate obtained by the preparation by adopting XRD (X-ray diffraction) XRF (X-ray fluorescence spectrum), FTIR (Fourier transform infrared spectrum), TG-DTG (thermogravimetric analysis), SEM (scanning electron microscope) and the like. The combined XRD and FTIR results showed that the precipitate was mainly struvite combined with organic matter to form a complex (fig. 1a, fig. 1 b), with an organic content of 24.23 wt% (fig. 1c), and the mineral chemical composition was as follows by XRF analysis: p 2 O 5 47.76％、MgO 43.45％、CaO 2.34％、Na 2 O 1.22％、SiO 2 0.46％、K 2 O0.26% and the other 4.51%. The biogenic struvite is porous on the surface, mostly irregular in shape, and can form spherical porous laminated characteristic aggregates (figure 1d), the surface of the struvite is mainly negatively charged, and the Zeta potential is (-17.53 +/-1.01) mV.
Example 2:
influence of different addition amounts of adsorbents on adsorption performance of biogenic struvite:
0.005 g, 0.01 g, 0.03 g, 0.05g, 0.07 g, and 0.1g of a bio-sourced struvite sample (prepared in example 1) were weighed, and adsorption experiments were performed in a centrifuge tube containing Cd (400mg/L) and Cu (400mg/L) solutions (20mL, pH 5.0), and the tube was placed in a shaker at 100r/min and 25 ℃ for 24 hours, and 3 replicates were set for each experiment. And centrifuging at 8000r/min for 15min after adsorption is finished to obtain supernatant, and measuring the concentration of various heavy metal ions in the supernatant by adopting an AAS method. Q e And A e Can be calculated by the formulas (2.1) and (2.2), respectively.
In the formula: c i As the concentration of the starting metal ion (mg/L), C e For the concentration of metal ions (mg/L) at equilibrium for adsorption, W is the mass of the adsorbent (g), V is the adsorptionVolume (L), Q) of the system metal ion concentrate e The amount of metal ions (mg/g) adsorbed at equilibrium for adsorption was determined.
The effect of the addition amount of the biogenic struvite on the adsorption efficiency is shown in fig. 2a, and it can be seen that the adsorption efficiency is continuously improved along with the increase of the dosage of the biogenic struvite. This is probably due to the fact that an increase in the amount of adsorbent used results in an increase in the specific surface area of the adsorbent, thereby providing more adsorption sites for heavy metals. When the addition amount of the biological source struvite is 2.5g/L, the adsorption efficiency of the biological source struvite on Cd (initial concentration: 400mg/L) and Cu (initial concentration: 400mg/L) is the highest (about 90%), and the adsorption efficiency does not change significantly with the increase of the addition amount of the biological source struvite, and 2.5g/L is the optimal addition amount of the biological source struvite. Meanwhile, we found that the adsorption amount of the biogenic struvite is decreased continuously with the increase of the addition amount of the biogenic struvite (fig. 2b), which is caused by the unsaturated adsorption sites in the adsorption reaction with the increase of the dosage of the adsorbent. Another reason may be that the tendency of the adsorbent to aggregate at high adsorbent concentrations results in a reduction in the total surface area of biogenic struvite and an increase in the diffusion path length.
Example 3:
adsorption characteristics of biogenic struvite to heavy metals and comparison:
the biogenic struvite prepared in example 1 above was used for heavy metal adsorption: the bio-sourced struvite prepared above was added to heavy metal (Cd, Cu) simulated wastewater with different concentrations (10-1000mg/L, pH 5.0) according to the amount of 2.5g/L of adsorbent, and adsorbed in a shaker at 25 ℃ and 100rpm for 24 h. Centrifuging (8000rpm, 10min) after adsorption, measuring the concentration of each heavy metal ion by atomic absorption spectrometry, and calculating to obtain the adsorption efficiency A of biological source struvite to heavy metal e (%) (formula 2.1) and adsorption Q e (mg/g) (equation 2.2). The adsorption data was further analyzed using Langmuir (equation 3.1) and F reundlich (equation 3.2) isothermal adsorption models.
In the formula: q max Maximum adsorption capacity (mg/g) of the adsorbent for heavy metal ions; k L Adsorption coefficient (L/mg) for Langmuir model; k F And n are parameters of the Freundlich model relating to the adsorption amount and the adsorption strength, respectively.
By comparing R 2 The values show that the Langmuir isothermal adsorption model has a better fitting effect (Table 1), and the adsorption of the biogenic struvite prepared in example 1 is mainly of a monomolecular adsorption type. Maximum adsorption amounts (Q) of Cd (II) and Cu (II) by the biogenic struvite prepared in example 1 max ) Respectively as follows: 357.143 and 344.828mg/g, The maximum adsorption capacity of The biological adsorbent is obviously higher than that of struvite (The phase transformation of microbial induced structure and its Cd (II) immobilization mechanism) induced and synthesized by other microbial strains and other common mineral adsorbents (Table 2), in addition, even in a water body with Cd (II) and Cu (II) composite pollution (400mg/L), The adsorption efficiency of The biological source struvite prepared in The example 1 on Cd (II) and Cu (II) is about 90%, and The two heavy metals can be removed simultaneously; therefore, the biological source struvite is utilized to remove or passivate heavy metals in polluted water or soil, and has great application potential. Although some materials (e.g., chitosan/TiO) 2 Composite material) has a greater Q than biogenic struvite max (table 2), but the preparation cost of the compounds is higher than that of biological source guano stone, the environment is not friendly, the preparation method is more complex, and the large-scale popularization and use are not facilitated.
TABLE 1 Langmuir and Freundlich model parameters
TABLE 2 maximum adsorption capacity (Q) of different adsorbing materials to Cd (II) and Cu (II) max Comparison of mg/g)
Example 4:
influence of different pH on adsorption properties of biogenic struvite:
0.05g of the biogenic struvite obtained in example 1 was weighed into a 50mL centrifuge tube, and 20mL of heavy metal concentrates (Cd: 400mg/L, Cu: 400mg/L) with different pH values (1-8) were added, respectively. Mixing, and adsorbing in a shaking table at 25 deg.C and 100rp m for 24 hr. After adsorption, centrifugally collecting each group of supernatant, measuring the concentration of each metal ion by adopting an atomic absorption spectrophotometry, and calculating the adsorption efficiency A of each group of supernatant e (%) (equation 2.1). The result shows that the biological source struvite still can keep higher adsorption capacity and is basically not influenced by an acid environment (pH is 3) when the pH is more than or equal to 3 (figure 3), which shows that the biological source struvite has better acid resistance and the adsorption performance is basically not influenced by the pH of the environment.
Example 5:
the influence of different time on the adsorption performance of the biological source struvite and the adsorption kinetic process thereof:
0.05g of the biogenic struvite prepared in example 1 is fully and uniformly mixed with a heavy metal ion Cd (400mg/L) solution (20mL, pH is 5.0), and then the mixture is placed in a shaking table at 100r/min and 25 ℃ for shaking for different time t (1-1440 min), wherein 3 parallels are arranged in each group. Centrifuging (12000r/min, 1min) after adsorption is finished to obtain supernatant, and measuring the concentration of heavy metal ions in the supernatant by adopting an A AS method. The adsorption capacity (Q) after adsorbing for different time t can be calculated by the formula 5.1 t Mg/g) (equation 5.1) and adsorption efficiency A e (equation 2.1):
in the formula: c i And C t Respectively represent the initial concentration of heavy metal ions and the equilibrium concentration (mg/L) after adsorption t (min), V represents the volume (L) of the adsorption solution, and M represents the mass (g) of the adsorbent.
The adsorption kinetics can provide important information about the adsorption mechanism, and the kinetic adsorption data of the adsorbent can be analyzed by utilizing a pseudo first-order (formula 5.2) and a pseudo second-order (formula 5.3) adsorption kinetics model, so that the kinetic adsorption characteristics can be further known:
Ln(Q e,exp –Q t )＝Ln(Q e1,cal )–K 1 t (equation 5.2)
In the formula: k 1 Represents the pseudo first order adsorption rate constant (min) -1 )，Q e,exp Refers to the adsorption capacity (mg/g) of heavy metal ions when the adsorption reaches the equilibrium; q e1,cal Represents the amount of heavy metal ions (mg/g) adsorbed at equilibrium, as calculated from the pseudo first order adsorption kinetics equation. Likewise, K 2 Represents the pseudo-second order adsorption rate constant (g/mg. min.), Q e2,cal Represents the amount (mg/g) of the heavy metal ions adsorbed at equilibrium, as calculated from the pseudo-second order adsorption kinetics equation.
The result shows that the adsorption efficiency of the biogenic struvite on Cd (II) and Cu (II) is rapidly increased in the first 60min (figure 4 a); with the extension of time, the adsorption efficiency does not change obviously, and finally the adsorption efficiency of the biological source struvite to Cd (II) and Cu (II) is respectively stabilized as follows: 90% and 86% or so. The kinetic data were analyzed using pseudo-primary and pseudo-secondary adsorption kinetic models and the corresponding kinetic parameters were calculated (fig. 4b and 4 c). The results show that the pseudo-second order adsorption kinetics model has a higher correlation coefficient (R) than the pseudo-first order adsorption kinetics model 2 > 0.99) and the amount of adsorption (Q) obtained was calculated from a pseudo-secondary adsorption kinetic model e2,cal ) More closely approximate the amount of adsorption (Q) obtained in the experiment e ) (ii) a The absorption kinetic process between the struvite with the biological source and the heavy metal ions can be more accordant with the pseudoA secondary adsorption kinetic model, which shows that the adsorption rate depends on the number of unoccupied adsorption sites on the adsorbent surface, and the adsorption process is dominated by chemisorption.
Example 6:
influence of different temperatures on the adsorption properties of biogenic struvite:
0.05g of the biogenic struvite obtained in example 1 was thoroughly mixed with 20mL of a heavy metal ion Cd (500mg/L) and Cu (500mg/L) solution (pH 5). The mixture was placed in a shaker at 100r/min for 24h at different temperatures (10, 25, 40 and 55 ℃) and 3 replicates were set up for each experiment. After adsorption, the supernatant was collected by centrifugation (8000r/min, 15min), the concentration of each metal ion in the supernatant was measured by AAS method, and the adsorption efficiency (A) was calculated by the formula (3.1) e ). The result shows that, as shown in fig. 5, the maximum adsorption efficiency of biogenic struvite on cd (ii), cu (ii) can reach about 85%, and the adsorption efficiency increases with the increase of temperature, which indicates that the adsorption process is an endothermic reaction. The increase in temperature that results in the enhanced adsorption capacity of biologically derived struvite may be due to the temperature increase expanding the pore structure of the mineral and activating active sites on the surface of the mineral material. It can be seen that the increase of the adsorption temperature is beneficial to the adsorption of heavy metal ions by the biogenic struvite.
Example 7:
the operation method for calculating the biological source struvite required by the polluted wastewater (ammonia nitrogen concentration is 100mg/L) of 1 ton of rare earth mining area heavy metals Cd (II), Cu (II) (concentration is 1mg/L, pH is 5.0):
(1) seed liquid preparation
The 200mL LB medium components are: 2g of tryptone, 1g of yeast extract and 2g of NaCl, and adding water to a constant volume of 200mL, wherein the pH value is 7.0. Sterilizing at 115 deg.C for 30min, inoculating 1-2 ring Bacillus licheniformis (CGMCC No.24275) with inoculating loop, culturing at 30 deg.C and 180rpm for 10 hr to obtain strain liquid [ 3.85 + -0.49 ] x 10 8 cfu/mL】。
(2) Amplification culture and induced synthesis of biogenic struvite
The amount of biogenic struvite required was 2.8g calculated from the maximum adsorption amount (357.14mg/g) of biogenic struvite to Cd (II). Struvite according to biological sourceThe amount of biogenic struvite required was calculated to be 2.9g for the maximum adsorption amount (344.83mg/g) of Cu (II). The seed solution was inoculated into 5L of LB broth (containing 5g of MgCl) in an amount of 2% 2 ) Culturing at 30 deg.C and 180rp m for 7 days, and centrifuging to obtain precipitate as biological source struvite sample.
The using method comprises the following steps: the obtained biological source struvite sample is added into 1 ton of wastewater and fully and uniformly stirred, metal ions in the wastewater can be removed after 2 hours, and the efficiency is over 90 percent. The heavy metal adsorption material prepared by the invention has the advantages of large adsorption capacity, low preparation cost, acid resistance, short adsorption time, good stability, environmental friendliness and good application prospect.
The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the above embodiment, and the present invention shall fall within the protection scope of the present invention as long as the technical effects of the present invention are achieved by the same means. The invention is capable of other modifications and variations in its technical solution and/or its implementation, within the scope of protection of the invention.
Claims (8)
1. A preparation method of biogenic minerals for treating heavy metal wastewater in a rare earth mining area is characterized by comprising the following steps: inoculating bacillus licheniformis LRL007 into a liquid culture medium containing soluble magnesium salt for culture to obtain the biogenic mineral; the bacillus licheniformis LRL007 has been preserved in the common microorganism center of China Committee for culture Collection of microorganisms at 10.1.2022, the preservation address is No. 3 of West Lu No. 1 of Beijing Kogyo, the rising area of Beijing, and the preservation number is CGMCC No. 24275.
2. The production method according to claim 1, wherein the liquid medium is an LB medium or a beef extract peptone medium; the addition amount of the soluble magnesium salt is 0.5-1 g/L.
3. The method of claim 1, wherein the bacillus licheniformis LRL007 is inoculated by: adding 2-5 mL of seed liquid into every 1000mL of culture medium, wherein the ground in the seed liquidThe concentration of the Bacillus licheniformis LRL007 is (8-38) multiplied by 10 7 cfu/mL。
4. The preparation method according to claim 1, wherein the temperature in the culture process is 30-37 ℃ and the time is 72-168 hours; and after the culture is finished, drying the precipitate to obtain the biogenic mineral.
5. The method of claim 1, wherein the soluble magnesium salt is magnesium chloride.
6. A biogenic mineral for treating heavy metal wastewater in a rare earth mining area, which is characterized by being prepared by the preparation method of any one of claims 1 to 5.
7. The biogenic mineral according to claim 6, wherein the biogenic mineral has a mineral composition in terms of elemental oxide percentage as follows: p 2 O 5 47.76％、MgO 43.45％、CaO 2.34％、Na 2 O 1.22％、SiO 2 0.46％、K 2 O0.26% and the other 4.51%.
8. The biogenic mineral according to claim 6, wherein the Zeta potential of the biogenic mineral surface is-17.53 ± 1.01mV when the pH is 5.0.
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