CN109517753A - Biological vaterite and its preparation method and application - Google Patents
Biological vaterite and its preparation method and application Download PDFInfo
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- CN109517753A CN109517753A CN201811353239.1A CN201811353239A CN109517753A CN 109517753 A CN109517753 A CN 109517753A CN 201811353239 A CN201811353239 A CN 201811353239A CN 109517753 A CN109517753 A CN 109517753A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4868—Cells, spores, bacteria
-
- 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
- C02F2101/20—Heavy metals or heavy metal 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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention discloses a kind of biological vaterites and its preparation method and application.Bacillus subtilis is inoculated in the fluid nutrient medium containing soluble calcium salt and is cultivated, isolated biology vaterite after culture.Biological vaterite of the invention is the vaterite organic complex with porous laminated feature using bacillus subtilis induction synthesis, there is excellent adsorption capacity to heavy metal, to the maximal absorptive capacity of Cd (II), Pb (II), Ni (II) and Cu (II) respectively up to 172.41,769.23,270.27,178.57mg/g;Biological vaterite of the invention is more stable under acidic environment, has good buffer capacity, and good stability and heavy metal adsorption characteristic, preparation method simple economy environmental protection are still able to maintain in the environment of pH value is more than or equal to 3.
Description
Technical field
The present invention relates to heavy-metal adsorption materials more particularly to a kind of biological vaterite and its preparation method and application.
Background technique
Since heavy metal production requirement is significantly increased and increasingly strict environmental requirement, global heavy metal pollution problem are standby
It is concerned.The point exceeding standard rate of China's heavy metal pollution of soil is about 16.1%, and the cadmium paddy and cadmium wheat occurred in the recent period is
Cause the fear that the public is food-safe, heavy metal pollution seriously threatens the food safeties such as the grain in China.Heavy metal ion
Cd (II), Pb (II), Ni (II), Cu (II) etc. are the most common toxic pollutants in industrial wastewater, these heavy metals are arranged at present
The quantity being put into environment is also being continuously increased.Existing several processing methods can reduce the concentration of heavy metal in waste water, including
The precipitation method, electrodialysis, ion exchange, solvent extraction is reverse osmosis, UF membrane, and the methods of absorption.
Currently used absorption method is a kind of simple and easy heavy metal ion-containing waste water processing method, absorbing process letter
It is single easily operated, there is practicability, therefore be widely applied in terms of wastewater treatment.And the key of the technology is adsorption material
Material, the selection of existing adsorbent is very limited, while that there is also adsorption capacities is low, and the heavy metal ion of absorption is insecure, is easy
Desorption, leads to the problem that adsorption rate is low.With the aggravation of China's heavy metal pollution and increasingly strict, the hair of heavy metals emission standard
A kind of pollution control of the high novel adsorption agent material counterweight metal of bright absorption stability has positive meaning.Carbon in environment
Hydrochlorate mineral can be used for the removal of heavy metal ion, however, natural whiting is very low to the adsorption efficiency of heavy metal.About biology
Source vaterite-type calcium carbonate has not been reported the absorption of heavy metal, is worth further research and development.
Summary of the invention
Goal of the invention: aiming at the problems existing in the prior art, an object of the present invention is to provide a kind of biological ball graupel
Stone provides a kind of new and effective heavy metal absorbent;The second object of the present invention is to provide the preparation of the biology vaterite
Methods and applications.
Technical solution:
A kind of preparation method of biology vaterite, comprising: bacillus subtilis is inoculated in the liquid containing soluble calcium salt
It is cultivated in culture medium, isolated biology vaterite after culture.
The fluid nutrient medium is LB culture medium or beef extract-peptone culture.
The concentration of the soluble calcium salt is 6~16g/L, is further 8~16g/L.
The soluble calcium salt is calcium chloride.
The bacillus subtilis can be selected from the strains A CCC from Chinese agriculture Microbiological Culture Collection administrative center
01185, but it is not limited only to this, other bacillus subtilis strains can also be used, can equally achieve the effect that of the invention, example
Such as, the bacillus subtilis CGMCC 1.7740 of China General Microbiological culture presevation administrative center or the purchase of other commercial sources
The bacterial strain bought.
The inoculum concentration of the bacillus subtilis are as follows: 2~5mL seed liquor is added in every 100mL culture medium, it is withered in seed liquor
The concentration of careless bacillus is (6~9) × 107Cfu/mL or so.
The temperature of the culture is 30~37 DEG C, and the time is 72~168h;After culture, precipitating is collected, is obtained after dry
Biological vaterite.
The present invention also provides the biological vaterites that the preparation method is prepared.
The present invention also provides the biological vaterites in heavy metal adsorption or to prepare in heavy metal absorbent
Using.
Wherein heavy metal includes but are not limited to one or more of Cd, Pb, Ni, Cu.
The present invention also provides a kind of heavy metal absorbents, including the biological vaterite.
The utility model has the advantages that
Biological vaterite of the invention is functional microbial fertilizer bacterial strain-bacillus subtilis common using China
The vaterite organic complex with porous laminated feature of (Bacillus subtilis) induction synthesis, is containing vaterite
Calcium carbonate, bacterial chip and its metabolite joint product, be that having of developed based on biological mineralization machanism is efficient
The biogenic mineral material of heavy metal adsorption characteristic.
Biological vaterite of the invention has excellent adsorption capacity to heavy metal, to heavy metal Cd (II), Pb (II), Ni
(II) and the maximal absorptive capacity of Cu (II) is respectively up to 172.41,769.23,270.27,178.57mg/g.
Biological vaterite of the invention is more stable under acidic environment, has good buffer capacity, is more than or equal to 3 in pH
In the environment of be still able to maintain good stability and heavy metal adsorption characteristic.
The preparation method of biology vaterite of the invention is economic and environment-friendly, operation simple and fast, it is at low cost, applied widely and
Obtained vaterite stability is good, has well-developed how mesoporous;Without adding any poisonous and harmful substance in synthesis process,
Therefore the biology vaterite product will not bring secondary pollution, to environment without any potential risk, have to the reparation of heavy metal
Preferable application prospect.
Detailed description of the invention
Fig. 1 is the structure and shape characteristic figure of the biological vaterite of embodiment 1;
Fig. 2 is influence of the concentration to the structure of biological vaterite of 3 calcium chloride of embodiment;
Fig. 3 is influence of the embodiment 4pH value to biological vaterite adsorptivity and structural stability;
The induction synthesis and its adsorption process schematic diagram to heavy metal that Fig. 4 is the biological vaterite of the present invention.
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention, after the present invention has been read, those skilled in the art are to various equivalences of the invention
The modification of form falls within the application range as defined in the appended claims.
Embodiment 1
Biological vaterite the preparation method is as follows:
1. prepared by seed liquor: having sterilized the LB liquid medium [(1% (m/ of tryptone of (115 DEG C of 20min) in 200mL
V), yeast extract 0.5% (m/V), NaCl 1% (m/V), 6.5≤pH≤7.5] in inoculation 2-3 ring bacillus subtilis (can
Purchased from Chinese agriculture Microbiological Culture Collection administrative center, strain number: ACCC 01185), it is placed in the shaking table of 30 DEG C, 180rpm
To prepare bacterium seed liquor, [bacterial concentration is 8 × 10 to middle shaken cultivation 10h7Cfu/mL or so].
2. expanding culture and the induction synthesis of biological vaterite: 100mL is added in clean 250mL conical flask and contains
CaCl2The LB liquid medium of (0.8g).It is inoculated with 2mL bacterium seed liquor after 115 DEG C of sterilizing 20min, is arranged 30 in parallel, in 30
DEG C, 180rpm shaken cultivation 7 days to be to induce the formation of biological vaterite.
3. the collection of biological vaterite: fermentation liquid is centrifuged 15min through 8000rpm;The precipitating obtained will be collected and be placed in 55 DEG C
Baking oven in dry after grind, for use.
4. using XRD (X-ray diffraction), FTIR (Fourier transform infrared spectrum) and SEM-EDS (scanning electron microscope-energy
Spectrum) etc. the structure and pattern of above-mentioned preparation gained sediment are identified.In conjunction with XRD and FTIR the result shows that precipitating owner
The complex (a, b in Fig. 1) formed is combined for vaterite and organic matter.Spherical and other random carbon can be observed in SEM
Sour calcium, porous surface, and can the glomerate porous laminated feature aggregation (c1~c4 in Fig. 1) of shape.
Embodiment 2
Characterization of adsorption of the biological vaterite to heavy metal:
The absorption of heavy metal is used for using the biological vaterite prepared in above-described embodiment 1: according to the adsorbent of 2.5g/L
The biological vaterite of above-mentioned preparation is separately added into the heavy metal (Cd, Pb, Ni, Cu) of various concentration (10-610mg/L) by dosage
In simulated wastewater, adsorbed for 24 hours in the shaking table of 25 DEG C of 100rpm.It is centrifuged (8000rpm, 15min) after absorption, using atom
Absorption spectrometry measures the concentration of each heavy metal ion, and calculating acquires biological vaterite to the adsorption rate (%) of heavy metal (see public affairs
Formula (1)) and adsorbance (mg/g) (see formula (2)).Its adsorption number is analyzed using Langmuir Adsorption Model (see formula (3))
According to biological vaterite can be acquired to the maximal absorptive capacity Q of heavy metal ionmax(mg/g), the results are shown in Table 1.
In formula: CiFor the concentration (mg/L) of starting metals ion, CeConcentration (the mg/ of metal ion when reaching balance to adsorb
L), W is the quality (g) of adsorbent, and V is the volume (L) of absorption system metal ion dope, QeMetal when reaching balance for absorption
The adsorbance (mg/g) of ion, QmaxFor the maximal absorptive capacity (mg/g) of adsorbent, KLFor Langmuir absorption constant.)
Maximal absorptive capacity of the biological vaterite of table 1 to heavy metal
Embodiment 3
Influence of the concentration of calcium chloride to the structure and adsorptivity of biological vaterite:
1. preparing each 100mL of calcium chloride LB liquid medium of low concentration (2g/L) and high concentration (8g/L), 115 DEG C of sterilizings
2mL bacterium seed liquor is respectively inoculated with after 20min, every group setting 30 parallel, in 30 DEG C, 180rpm shaken cultivation 7 days to induce life
The formation of object vaterite, using the difference of its crystal structure of XRD analysis.As shown in Fig. 2, the master of low concentration calcium chloride induced synthesis
It to be amorphous calcium carbonate, and high calcium chloride concentration induced synthesis is vaterite calcium carbonate, illustrates that the concentration of calcium chloride can
The structure for influencing biological vaterite, only just can induce the formation of vaterite, most when the concentration of calcium chloride is more than or equal to 6g/L
The optimum concentration range of calcium chloride is determined eventually are as follows: 6-16g/L.Calcium chloride concentration then forms amorphous calcium carbonate lower than 6g/L, and
Concentration can then inhibit the growth of bacterium higher than 16g/L.
2. amorphous calcium carbonate will be prepared in 1. and biological vaterite is used for the absorption of heavy metal Cd, Pb, Ni, Cu,
Specific adsorption method referring to the method adsorbed in embodiment 2, can acquire amorphous calcium carbonate and biology vaterite to heavy metal Cd,
The maximal absorptive capacity of Pb, Ni, Cu.As a result, it has been found that the maximal absorptive capacity of biological vaterite will be significantly higher than the suction of amorphous calcium carbonate
Attached amount (as shown in table 2), this illustrates that the concentration of calcium chloride not only will affect the structure of biological vaterite, also will affect its adsorptivity
Energy.
The comparison of 2 amorphous calcium carbonate of table and biological vaterite maximal absorptive capacity
Embodiment 4
The stability of biological vaterite in acid condition and the characterization of adsorption to heavy metal:
Biological vaterite obtained in 0.05g embodiment 1 is weighed in 50mL centrifuge tube, is separately added into 20mL difference pH
The heavy metal dope (Cd:131mg/L, Pb:218mg/L, Ni:115mg/L, Cu:194mg/L) of (1-8).It mixes well and is placed on
25 DEG C, adsorb for 24 hours in the shaking table of 100rpm.After absorption, each group supernatant is collected by centrifugation, using atomic absorption spectrphotometry
Method measures the concentration of each metal ion, calculates its adsorbance (mg/g).The result shows that biological vaterite still may be used in pH >=3
To keep higher adsorption capacity, (a in Fig. 3) is not influenced by acidity (such as pH=3) environment substantially, illustrates biological vaterite tool
There is preferable acid-fast ability, and biology vaterite can also be stabilized (b in Fig. 3) in pH=3.
Embodiment 5
The production method of biology vaterite needed for calculating 1 ton of heavy metal Cd, Pb, Ni, Cu waste water (concentration is 1ppm):
(1) prepared by seed liquor
200mL LB medium component are as follows: tryptone 2g, yeast extract 1g, NaCl 2g add water to be settled to 200mL,
PH=7.0.115 DEG C of sterilizing 20min, after accessing 1-2 ring bacillus subtilis with oese, 30 DEG C, 180rpm cultivates 10h, obtains
Obtaining seed liquor, [bacteria concentration is 8 × 107cfu/mL]。
(2) expand culture and the induction synthesis of biological vaterite
It is according to the amount that maximal absorptive capacity (172.41mg/g) of the biological vaterite to Cd calculates required biological vaterite
5.8g.The amount of biological vaterite needed for calculating according to maximal absorptive capacity (769.23mg/g) of the biological vaterite to Pb is 1.3g.
The amount of biological vaterite needed for calculating according to maximal absorptive capacity (270.23mg/g) of the biological vaterite to Ni is 3.7g.According to life
Object vaterite amount of biological vaterite needed for calculating the maximal absorptive capacity (178.57mg/g) of Cu is 5.6g.With 110mL seed
Liquid is inoculated into second level LB culture solution 5.5L (CaCl containing 44g2) in, it 30 DEG C, is cultivated 7 days in 180rpm, centrifugation obtains sediment and is
For biological vaterite sample.
Application method: gained biology vaterite sample is added into 1 ton of waste water and is stirred, can will be given up after 2h
Metal ion removal in water, efficiency is 95% or more.Heavy metal ion adsorbing material adsorption capacity produced by the present invention is big, inhales
Attached performance is good, it is not easy to solve adsorption desorption, have broad application prospects.
Claims (10)
1. a kind of preparation method of biology vaterite characterized by comprising being inoculated in bacillus subtilis containing solubility calcium
It is cultivated in the fluid nutrient medium of salt, isolated biology vaterite after culture.
2. the preparation method of biology vaterite according to claim 1, which is characterized in that fluid nutrient medium is LB culture medium
Or beef-protein medium.
3. the preparation method of biology vaterite according to claim 1, which is characterized in that the concentration of soluble calcium salt is 6
~16g/L.
4. the preparation method of biology vaterite according to claim 1 or 3, which is characterized in that soluble calcium salt is chlorination
Calcium.
5. the preparation method of biology vaterite according to claim 1, which is characterized in that the inoculum concentration of bacillus subtilis
Are as follows: 2~5mL seed liquor is added in every 100mL culture medium, in seed liquor the concentration of bacillus subtilis be (6~9) ×
107Cfu/mL or so.
6. it is according to claim 1 biology vaterite preparation method, which is characterized in that the temperature of the culture be 30~
37 DEG C, the time is 72~168h;After culture, precipitating is collected, obtains biological vaterite after dry.
7. the biological vaterite that any one preparation method is prepared according to claim 1~6.
8. biology vaterite according to claim 7 is in heavy metal adsorption or prepares answering in heavy metal absorbent
With.
9. application according to claim 8, which is characterized in that heavy metal includes one or more of in Cd, Pb, Ni, Cu.
10. a kind of heavy metal absorbent, which is characterized in that including biological vaterite as claimed in claim 7.
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Cited By (2)
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CN111154810A (en) * | 2020-01-16 | 2020-05-15 | 南京师范大学 | Mineral biological modification method for holding lead ions under acidic condition, modified mineral material and application |
CN113275374A (en) * | 2021-05-28 | 2021-08-20 | 安徽农业大学 | Method for curing heavy metal by combining carbonate mineralized bacteria and hydroxyapatite |
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CN113275374A (en) * | 2021-05-28 | 2021-08-20 | 安徽农业大学 | Method for curing heavy metal by combining carbonate mineralized bacteria and hydroxyapatite |
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