CN110156060A - A method of calcite and vaterite phase co-conversion are controlled using calcium source concentration - Google Patents
A method of calcite and vaterite phase co-conversion are controlled using calcium source concentration Download PDFInfo
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- CN110156060A CN110156060A CN201910411312.4A CN201910411312A CN110156060A CN 110156060 A CN110156060 A CN 110156060A CN 201910411312 A CN201910411312 A CN 201910411312A CN 110156060 A CN110156060 A CN 110156060A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention discloses a kind of methods using calcium source concentration control calcite and vaterite phase co-conversion, comprising steps of Pasteur's sporosarcina (S.pasteurii) is inoculated on culture medium；Configure the nutrient salt solution of urea and a water calcium acetate；Urase solution is configured, urase solution is added in nutrient salt solution；Bacterium solution is added in urase and nutrition mixed salt solution；Ultrasonication 30min~1h at 20~40 DEG C obtains suspension；Suspension is poured into centrifuge tube, after 4000rpm centrifugation, outwells supernatant liquor, deionized water washing is added；Wash unreacted water calcium acetate；White particle sediment after centrifugation is placed in drying box and is dried, the calcium carbonate of different compositions and pattern is obtained.The present invention only changes the concentration of calcium source, realizes calcium carbonate and is continuously changed from calcite structure to vaterite structure, in calcium source concentration a certain range, calcite and vaterite coexist, the present invention is low to environmental condition requirement, and other reagents used are environmentally friendly, and experimental result repeatability is high.
Description
Technical field
The invention belongs to the technical field of biomimetic material more particularly to a kind of utilization calcium source concentration control calcites and ball graupel
The method of stone phase co-conversion.
Background technique
In nature, calcium carbonate is a kind of most common biomineralization material, is animal skeleton, shell, coral etc.
Important component.Calcium carbonate is very widely used in the industry, is a kind of important inorganic industrial additive, in food, makes
The fields such as paper, coating, rubber can improve the performances such as bulkiness, glossiness, brightness, mobility, the intensity of product.
There are many structure of calcium carbonate, can be divided into Carbon Dioxide calcium and aqueous carbonic acid calcium according to whether containing the crystallization water.Nothing
There are three types of crystal forms for aqueous carbonate calcium crystal tool: calcite, aragonite and vaterite.The physical and mechanical property difference of different crystal system calcium carbonate
Larger, and calcite phase ratio, vaterite has many advantages, such as that large specific surface area, specific gravity be small, good biocompatibility.In microorganism induction
During calcium carbonate repairing concrete crack and ground historical relic crack, vaterite has higher mobility than calcite and fills out
Filling property, and plural gel can be formed with the hydrated product of cement-hydrated calcium silicate, significantly improve concrete intensity and
Durability.Vaterite belongs to metastable phase, and vaterite can be converted into calcite by the short period in wet environment, further
Improve the mechanical strength for repairing crack.Therefore, by changing the relative amount of calcite and vaterite, the stream of slurry can be adjusted
Dynamic property, filling rate and mechanical strength, to significantly improve the repairing effect in concrete crack and ground historical relic crack.This is just needed
A kind of method that can control calcite and vaterite transformation is studied, the content of calcite and vaterite is continuously adjusted in realization
Control.
Existing literature or patent obtain mostly by the way that the additives such as surfactant, organic macromolecule are added with single
The vaterite micro-nano granules of pattern.Currently, about the method using calcium source concentration control calcite and vaterite phase co-conversion
It has not been reported.
Summary of the invention
Based on the above the deficiencies in the prior art, technical problem solved by the invention is to provide a kind of utilization calcium source concentration
The method for controlling calcite and vaterite phase co-conversion obtains the relative amount and shape that can continuously regulate and control calcite and vaterite
The method of looks.
In order to solve the above-mentioned technical problem, the present invention is achieved through the following technical solutions: the present invention provides a kind of utilization
The method of calcium source concentration control calcite and vaterite phase co-conversion, comprising the following steps:
S10: Pasteur's sporosarcina (S.pasteurii) is inoculated on culture medium, at 30 DEG C, the vibration of 100r/min
It swings and cultivates 48h in incubator, obtain bacterium solution；
S20: the mixed solution of configuration urea and a water calcium acetate is nutrient salt solution, and wherein urea concentration is 0.5mol/
L, a water calcium acetate concentration range are 0.025mol/L~1mol/L；
S30: configuration 0.2g/L urase solution, urease activity are 92~137u/mg, and nutrient salt solution is added in urase solution
In, nutrient salt solution and urase liquor capacity ratio are 8~9:1；
S40: bacterium solution is added in urase and nutrition mixed salt solution, and bacterium solution and mixed liquor volume ratio are 1:9~10,
Concussion uniformly, stands 72h at 10~30 DEG C；
S50: ultrasonication 30min~1h at 20~40 DEG C, obtain suspension；
S60: suspension is poured into centrifuge tube, after 4000rpm centrifugation, outwells supernatant liquor, and deionized water washing is added；
S70: it repeats step S50 and step S60 three times, washes unreacted water calcium acetate；
S80: the white particle sediment after centrifugation is placed in 60 DEG C of drying boxes and is dried for 24 hours, different compositions and shape are obtained
The calcium carbonate of looks.
Preferably, the composition of the culture medium in the step 1 includes: 10~30g/L of yeast extract, ammonium sulfate 15g/L,
The pH of culture medium is 7~9.5.
Further, as a water acetic acid calcium concentration≤0.025mol/L, the calcium carbonate granule of acquisition is single water chestnut face
Body shape calcite；
As a water acetic acid calcium concentration >=1mol/L, the calcium carbonate granule of acquisition is single spherical vaterite；
When a water acetic acid calcium concentration therebetween when, the calcium carbonate granule of acquisition is the mixing of calcite and vaterite
Object, granule-morphology is rhombohedron shape, three kinds of spherical shape, spindle-type patterns coexist.
By upper, the method for the invention using calcium source concentration control calcite and vaterite phase co-conversion at least has as follows
The utility model has the advantages that
1, the concentration for only changing calcium source, realizes calcium carbonate and is continuously changed from calcite structure to vaterite structure, calcium source
Crystal structure of calcium carbonate is single calcite when concentration is very low, and crystal structure of calcium carbonate is single ball when calcium source is dense
Aragonite.
2, in calcium source concentration a certain range, calcite and vaterite are coexisted, rhombohedron shape, spherical shape, three kinds of spindle-type
Pattern particle coexists, be formed by it is whole finer and close, it is higher than the calcium carbonate mechanical strength of one-component.For microorganism mortar
Application in concrete crack is repaired and stone cultural artifact crack is repaired is laid a good foundation.
3, urease-producing microorganism and urase are used simultaneously, and urease-producing microorganism is conducive to the forming core of crystal, urase and calcium source
Equal substances form a large amount of calcites and vaterite in a short time, are conducive to Fast Filling crack, urease-producing microorganism is through too long
It is still active after time, can further filling pore and crack, be more suitable for concrete crack and repair and Shi Zhiwen
During object crack is repaired.
4, microorganism used therefor is widely distributed microorganism in soil in the present invention, environmental condition is required it is low, it is used its
Its reagent is environmentally friendly, and reaction speed is fast, simple process, and experimental result repeatability is high.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And it can be implemented in accordance with the contents of the specification, and in order to allow above and other objects, features and advantages of the invention can
It is clearer and more comprehensible, below in conjunction with preferred embodiment, and cooperates attached drawing, detailed description are as follows.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, the attached drawing to embodiment is simply situated between below
It continues.
Fig. 1 is the XRD spectra of different-shape calcium carbonate sample that the embodiment of the present invention 1~8 is prepared, wherein A in (a),
B, C, D diffraction spectral line respectively correspond the XRD spectra of the obtained sample of embodiment 1,2,3,4；(b) E, F, G, H diffraction spectral line in
Respectively correspond the XRD spectra of the obtained sample of embodiment 5,6,7,8；
Fig. 2 is the infrared spectrogram of different-shape calcium carbonate sample prepared by the embodiment of the present invention 1~8, wherein A in (a),
B, C, D diffraction spectral line respectively correspond the infrared spectrogram of sample obtained by embodiment 1,2,3,4；(b) E, F, G, H diffraction spectral line in
Respectively correspond the infrared spectrogram of sample obtained by embodiment 5,6,7,8；
Fig. 3 be the embodiment of the present invention 1~8 prepare different-shape calcium carbonate sample SEM picture, wherein figure (a), (b),
(c), (d), (e), (f), (g), (h) are respectively the SEM picture of calcium carbonate prepared by embodiment 1,2,3,4,5,6,7,8；
Fig. 4 is the flow chart of the invention that calcite and the method for vaterite phase co-conversion are controlled using calcium source concentration.
Specific embodiment
The embodiment of the invention will now be described in detail with reference to the accompanying drawings, and as part of this specification passes through
Embodiment illustrates the principle of the present invention, and other aspects of the present invention, feature and its advantage will become by the detailed description
It is very clear.In the attached drawing of institute's reference, the same or similar component is indicated using identical drawing reference numeral in different figures.
The Pasteur's sporosarcina used in the embodiment of the present invention derives from American Type Culture Collecti, number ATCC
11859.Pasteur's sporosarcina, is in Gram-positive, and appearance ellipse bar has gemma, no pod membrane.In temperature 4 DEG C~37
DEG C and pH7~9.5 in the range of, which can grow.
The urea used is the production of Mike woods company, molecular formula CH4N2O analyzes pure, purity 99%.
The water calcium acetate used is the production of Mike woods company, molecular formula C4H8CaO5, analyze pure, purity 98%.
The urase used is the production of TOYOBO company, Japan, activity 148u/mg.
The yeast extract used wins the production of microorganism Science and Technology Ltd., total nitrogen 11.57%, loss on drying for Shanghai
4.8%, ash content 9.5%, chloride is less than 6%, pH value 6.8 (2% solution).
For the ammonium sulfate used for Sinopharm Chemical Reagent Co., Ltd.'s production, molecular formula is (NH4)2SO4Analyze it is pure, it is pure
Degree 99%.
Utilization calcium source concentration control calcite of the invention and the mutual method of converting of vaterite, the constituent of sample are ball
Aragonite and calcite, vaterite are 0%~100% in content range wherein.
The present invention using calcium source concentration control calcite and vaterite phase co-conversion, when a water calcium acetate concentration≤
When 0.025mol/L, the content of vaterite is 0%, and the content of calcite is 100%, and the pattern for forming particle is rhombohedron shape,
Having a size of less than 15 μm；When the concentration of a water calcium acetate is when 0.025mol/L is between 1mol/L, the content of vaterite is 0%
Consecutive variations between~100%, the pattern for forming particle is that rhombohedron shape and spherical shape coexist, and size is less than 25 μm；When a water second
When concentration >=1mol/L of sour calcium, the content of vaterite is 100%, and the content of calcite is 0%, and the pattern for forming particle is ball
Shape, size is less than 10 μm.
The present invention is specifically described in detail below in conjunction with drawings and the specific embodiments.
Embodiment 1
Step 1: Pasteur's sporosarcina (S.pasteurii) is inoculated on culture medium, at 30 DEG C, 100r/min's
48h is cultivated in shaken cultivation case, obtains bacterium solution；Wherein, culture medium includes 10~30g/L of yeast extract, ammonium sulfate 15g/L,
The pH of culture medium is 7~9.5；
Step 2: the mixed solution of configuration urea and a water calcium acetate is nutrient salt solution, and wherein urea concentration is
0.5mol/L, a water acetic acid calcium concentration are 0.025mol/L；
Step 3: nutrient salt solution is added in urase solution by configuration 0.2g/L urase solution (urease activity 137u/mg)
In, nutrient salt solution and urase liquor capacity ratio are 9:1；
Step 4: bacterium solution is added in urase and nutrition mixed salt solution, bacterium solution and mixed liquor volume ratio are 1:10,
Concussion is uniform, in 20 DEG C of standing 72h；
Step 5: ultrasonication 30min~1h at 20~40 DEG C obtains suspension；
Step 6: suspension being poured into centrifuge tube, after 4000rpm centrifugation, supernatant liquor is outwelled, deionized water water is added
It washes；
Step 7: repeating step 5,6 three times, wash unreacted water calcium acetate；
Step 8: the white particle sediment after centrifugation is placed in 60 DEG C of drying boxes and is dried for 24 hours, obtain it is different composition and
The calcium carbonate of pattern.
Calcium carbonate prepared by the present embodiment 1 passes through XRD as a result, map A as shown in figure 1,2 θ values 23.3 °, 29.7 °,
36.3 °, 39.8 °, 43.5 °, 47.8 °, 48.9 ° there are calcite crystal form characteristic diffraction peak, in sample containing 100% calcite
Type calcium carbonate；By infared spectrum, can also be observed in 712cm in the map A in Fig. 2-1And 876cm-1There is-C-O-at place
The characteristic absorption peak of C-.It is observed by SEM, such as the figure (a) in Fig. 3, granule-morphology is rhombohedron shape, and particle size is less than 15 μ
m。
Embodiment 2
Step 1: Pasteur's sporosarcina (S.pasteurii) is inoculated on culture medium, at 30 DEG C, 100r/min's
48h is cultivated in shaken cultivation case, obtains bacterium solution；Wherein, culture medium includes 10~30g/L of yeast extract, ammonium sulfate 15g/L,
The pH of culture medium is 7~9.5；
Step 2: the mixed solution of configuration urea and a water calcium acetate is nutrient salt solution, and wherein urea concentration is
0.5mol/L, a water acetic acid calcium concentration are 0.1mol/L；
Step 3: nutrient salt solution is added in urase solution by configuration 0.2g/L urase solution (urease activity 137u/mg)
In, nutrient salt solution and urase liquor capacity ratio are 8:1；
Step 4: bacterium solution is added in urase and nutrition mixed salt solution, bacterium solution and mixed liquor volume ratio are 1:10,
Concussion is uniform, in 20 DEG C of standing 72h；
Step 5: ultrasonication 30min~1h at 20~40 DEG C obtains suspension；
Step 6: suspension being poured into centrifuge tube, after 4000rpm centrifugation, supernatant liquor is outwelled, deionized water water is added
It washes；
Step 7: repeating step 5,6 three times, wash unreacted water calcium acetate；
Step 8: the white particle sediment after centrifugation is placed in 60 DEG C of drying boxes and is dried for 24 hours, obtain it is different composition and
The calcium carbonate of pattern.
Calcium carbonate prepared by the present embodiment 2 passes through XRD as a result, map B as shown in figure 1,2 θ values 23.3 °, 29.7 °,
36.3 °, 39.8 °, 43.5 °, 47.8 °, 48.9 ° there are calcite crystal form characteristic diffraction peak, while 2 θ values 25.0 °, 27.3 °,
33.0 °, 44.1 °, 50.3 ° there are the diffraction maximums of vaterite crystal form feature, contain 82% calcite type calcium carbonate, 18% ball
Vaterite type calcium carbonate；By in infared spectrum, map B in Fig. 2 can also be observed in 712cm-1And 876cm-1The side of having, place solution
The absorption peak of stone, in 745cm-1And 872cm-1There is the absorption peak of vaterite at place.It is observed by SEM, such as the granulated in Fig. 3 (b)
Looks are that rhombohedron shape and spherical morphology coexist, and particle size is less than 20 μm.
Embodiment 3
Step 1: Pasteur's sporosarcina (S.pasteurii) is inoculated on culture medium, at 30 DEG C, 100r/min's
48h is cultivated in shaken cultivation case, obtains bacterium solution；Wherein, culture medium includes 10~30g/L of yeast extract, ammonium sulfate 15g/L,
The pH of culture medium is 7~9.5；
Step 2: the mixed solution of configuration urea and a water calcium acetate is nutrient salt solution, and wherein urea concentration is
0.5mol/L, a water acetic acid calcium concentration are 0.3mol/L；
Step 3: nutrient salt solution is added in urase solution by configuration 0.2g/L urase solution (urease activity 110u/mg)
In, nutrient salt solution and urase liquor capacity ratio are 9:1；
Step 4: bacterium solution is added in urase and nutrition mixed salt solution, bacterium solution and mixed liquor volume ratio are 1:10,
Concussion is uniform, in 10 DEG C of standing 72h；
Step 5: ultrasonication 30min~1h at 20~40 DEG C obtains suspension；
Step 6: suspension being poured into centrifuge tube, after 4000rpm centrifugation, supernatant liquor is outwelled, deionized water water is added
It washes；
Step 7: repeating step 5,6 three times, wash unreacted water calcium acetate；
Step 8: the white particle sediment after centrifugation is placed in 60 DEG C of drying boxes and is dried for 24 hours, obtain it is different composition and
The calcium carbonate of pattern.
Calcium carbonate prepared by the present embodiment 3 passes through XRD as a result, map C as shown in figure 1,2 θ values 23.3 °, 29.7 °,
36.3 °, 39.8 °, 43.5 °, 47.8 °, 48.9 ° there are calcite crystal form characteristic diffraction peak, while 2 θ values 25.0 °, 27.3 °,
33.0 °, 44.1 °, 50.3 ° there are the diffraction maximums of vaterite crystal form feature, contain 56% calcite type calcium carbonate, 44% ball
Vaterite type calcium carbonate；By in infared spectrum, map C in Fig. 2 can also be observed in 712cm-1And 876cm-1The side of having, place solution
The absorption peak of stone, in 745cm-1And 872cm-1There is the absorption peak of vaterite at place.It is observed by SEM, such as the granulated in Fig. 3 (c)
Looks are that rhombohedron shape and spherical morphology coexist, and particle size is less than 25 μm.
Embodiment 4
Step 1: Pasteur's sporosarcina (S.pasteurii) is inoculated on culture medium, at 30 DEG C, 100r/min's
48h is cultivated in shaken cultivation case, obtains bacterium solution；Wherein, culture medium includes 10~30g/L of yeast extract, ammonium sulfate 15g/L,
The pH of culture medium is 7~9.5；
Step 2: the mixed solution of configuration urea and a water calcium acetate is nutrient salt solution, and wherein urea concentration is
0.5mol/L, a water acetic acid calcium concentration are 0.5mol/L；
Step 3: nutrient salt solution is added in urase solution by configuration 0.2g/L urase solution (urease activity 100u/mg)
In, nutrient salt solution and urase liquor capacity ratio are 9:1；
Step 4: bacterium solution being added in urase and nutrition mixed salt solution, bacterium solution and mixed liquor volume ratio are 1:9, shake
It swings uniformly, in 20 DEG C of standing 72h；
Step 5: ultrasonication 30min~1h at 20~40 DEG C obtains suspension；
Step 6: suspension being poured into centrifuge tube, after 4000rpm centrifugation, supernatant liquor is outwelled, deionized water water is added
It washes；
Step 7: repeating step 5,6 three times, wash unreacted water calcium acetate；
Step 8: the white particle sediment after centrifugation is placed in 60 DEG C of drying boxes and is dried for 24 hours, obtain it is different composition and
The calcium carbonate of pattern.
Calcium carbonate prepared by the present embodiment 4 passes through XRD as a result, map D as shown in figure 1,2 θ values 23.3 °, 29.7 °,
36.3 °, 39.8 °, 43.5 °, 47.8 °, 48.9 ° there are calcite crystal form characteristic diffraction peak, while 2 θ values 25.0 °, 27.3 °,
33.0 °, 44.1 °, 50.3 ° there are the diffraction maximums of vaterite crystal form feature, contain 50% calcite type calcium carbonate, 50% ball
Vaterite type calcium carbonate；By in infared spectrum, map D in Fig. 2 can also be observed in 712cm-1And 876cm-1The side of having, place solution
The absorption peak of stone, in 745cm-1And 872cm-1There is the absorption peak of vaterite at place.It is observed by SEM, such as the granulated in Fig. 3 (d)
Looks are that rhombohedron shape and spherical morphology coexist, and particle size is less than 25 μm.
Embodiment 5
Step 1: Pasteur's sporosarcina (S.pasteurii) is inoculated on culture medium, at 30 DEG C, 100r/min's
48h is cultivated in shaken cultivation case, obtains bacterium solution；Wherein, culture medium includes 10~30g/L of yeast extract, ammonium sulfate 15g/L,
The pH of culture medium is 7~9.5；
Step 2: the mixed solution of configuration urea and a water calcium acetate is nutrient salt solution, and wherein urea concentration is
0.5mol/L, a water acetic acid calcium concentration are 0.6mol/L；
Step 3: nutrient salt solution is added in urase solution by configuration 0.2g/L urase solution (urease activity 120u/mg)
In, nutrient salt solution and urase liquor capacity ratio are 8:1；
Step 4: bacterium solution is added in urase and nutrition mixed salt solution, bacterium solution and mixed liquor volume ratio are 1:10,
Concussion is uniform, in 30 DEG C of standing 72h；
Step 5: ultrasonication 30min~1h at 20~40 DEG C obtains suspension；
Step 6: suspension being poured into centrifuge tube, after 4000rpm centrifugation, supernatant liquor is outwelled, deionized water water is added
It washes；
Step 7: repeating step 5,6 three times, wash unreacted water calcium acetate；
Step 8: the white particle sediment after centrifugation is placed in 60 DEG C of drying boxes and is dried for 24 hours, obtain it is different composition and
The calcium carbonate of pattern.
Calcium carbonate prepared by the present embodiment 5 passes through XRD as a result, map E as shown in figure 1,2 θ values 23.3 °, 29.7 °,
36.3 °, 39.8 °, 43.5 °, 47.8 °, 48.9 ° there are calcite crystal form characteristic diffraction peak, while 2 θ values 25.0 °, 27.3 °,
33.0 °, 44.1 °, 50.3 ° there are the diffraction maximums of vaterite crystal form feature, contain 33% calcite type calcium carbonate, 67% ball
Vaterite type calcium carbonate；By can also observe in 712cm in infared spectrum-1And 876cm-1There is the absorption peak of calcite at place,
745cm-1And 872cm-1There is the absorption peak of vaterite at place, such as the map E in Fig. 2.It is observed by SEM, such as the particle in Fig. 3 (e)
Pattern is rhombohedron shape, three kinds of spherical shape, spindle-type patterns coexist, and particle size is less than 20 μm.
Embodiment 6
Step 1: Pasteur's sporosarcina (S.pasteurii) is inoculated on culture medium, at 30 DEG C, 100r/min's
48h is cultivated in shaken cultivation case, obtains bacterium solution；Wherein, culture medium includes 10~30g/L of yeast extract, ammonium sulfate 15g/L,
The pH of culture medium is 7~9.5；
Step 2: the mixed solution of configuration urea and a water calcium acetate is nutrient salt solution, and wherein urea concentration is
0.5mol/L, a water acetic acid calcium concentration are 0.8mol/L；
Step 3: nutrient salt solution is added in urase solution by configuration 0.2g/L urase solution (urease activity 130u/mg)
In, nutrient salt solution and urase liquor capacity ratio are 9:1；
Step 4: bacterium solution is added in urase and nutrition mixed salt solution, bacterium solution and mixed liquor volume ratio are 1:10,
Concussion is uniform, in 10 DEG C of standing 72h；
Step 5: ultrasonication 30min~1h at 20~40 DEG C obtains suspension；
Step 6: suspension being poured into centrifuge tube, after 4000rpm centrifugation, supernatant liquor is outwelled, deionized water water is added
It washes；
Step 7: repeating step 5,6 three times, wash unreacted water calcium acetate；
Step 8: the white particle sediment after centrifugation is placed in 60 DEG C of drying boxes and is dried for 24 hours, obtain it is different composition and
The calcium carbonate of pattern.
Calcium carbonate prepared by the present embodiment 6 passes through XRD as a result, map F as shown in figure 1,2 θ values 23.3 °, 29.7 °,
36.3 °, 39.8 °, 43.5 °, 47.8 °, 48.9 ° there are calcite crystal form characteristic diffraction peak, while 2 θ values 25.0 °, 27.3 °,
33.0 °, 44.1 °, 50.3 ° there are the diffraction maximums of vaterite crystal form feature, contain 29% calcite type calcium carbonate, 71% ball
Vaterite type calcium carbonate；By in infared spectrum, map F in Fig. 2 can also be observed in 712cm-1And 876cm-1The side of having, place solution
The absorption peak of stone, in 745cm-1And 872cm-1There is the absorption peak of vaterite at place.It is observed by SEM, such as the granulated in Fig. 3 (f)
Looks are rhombohedron shape, three kinds of spherical shape, spindle-type patterns coexist, and particle size is less than 20 μm.
Embodiment 7
Step 1: Pasteur's sporosarcina (S.pasteurii) is inoculated on culture medium, at 30 DEG C, 100r/min's
48h is cultivated in shaken cultivation case, obtains bacterium solution；Wherein, culture medium includes 10~30g/L of yeast extract, ammonium sulfate 15g/L,
The pH of culture medium is 7~9.5；
Step 2: the mixed solution of configuration urea and a water calcium acetate is nutrient salt solution, and wherein urea concentration is
0.5mol/L, a water acetic acid calcium concentration are 0.9mol/L；
Step 3: nutrient salt solution is added in urase solution by configuration 0.2g/L urase solution (urease activity 92u/mg)
In, nutrient salt solution and urase liquor capacity ratio are 9:1；
Step 4: bacterium solution is added in urase and nutrition mixed salt solution, bacterium solution and mixed liquor volume ratio are 1:10,
Concussion is uniform, in 20 DEG C of standing 72h；
Step 5: ultrasonication 30min~1h at 20~40 DEG C obtains suspension；
Step 6: suspension being poured into centrifuge tube, after 4000rpm centrifugation, supernatant liquor is outwelled, deionized water water is added
It washes；
Step 7: repeating step 5,6 three times, wash unreacted water calcium acetate；
Step 8: the white particle sediment after centrifugation is placed in 60 DEG C of drying boxes and is dried for 24 hours, obtain it is different composition and
The calcium carbonate of pattern.
Calcium carbonate prepared by the present embodiment 7 passes through XRD as a result, map G as shown in figure 1,2 θ values 23.3 °, 29.7 °,
36.3 °, 39.8 °, 43.5 °, 47.8 °, 48.9 ° there are calcite crystal form characteristic diffraction peak, while 2 θ values 25.0 °, 27.3 °,
33.0 °, 44.1 °, 50.3 ° there are the diffraction maximums of vaterite crystal form feature, contain 16% calcite type calcium carbonate, 84% ball
Vaterite type calcium carbonate；By in infared spectrum, map G in Fig. 2 can also be observed in 712cm-1And 876cm-1The side of having, place solution
The absorption peak of stone, in 745cm-1And 872cm-1There is the absorption peak of vaterite at place.It is observed by SEM, such as the granulated in Fig. 3 (g)
Looks are rhombohedron shape, three kinds of spherical shape, spindle-type patterns coexist, and particle size is less than 20 μm.
Embodiment 8
Step 1: Pasteur's sporosarcina (S.pasteurii) is inoculated on culture medium, at 30 DEG C, 100r/min's
48h is cultivated in shaken cultivation case, obtains bacterium solution；Wherein, culture medium includes 10~30g/L of yeast extract, ammonium sulfate 15g/L,
The pH of culture medium is 7~9.5；
Step 2: the mixed solution of configuration urea and a water calcium acetate is nutrient salt solution, and wherein urea concentration is
0.5mol/L, a water acetic acid calcium concentration are 1mol/L；
Step 3: nutrient salt solution is added in urase solution by configuration 0.2g/L urase solution (urease activity 137u/mg)
In, nutrient salt solution and urase liquor capacity ratio are 8:1；
Step 4: bacterium solution being added in urase and nutrition mixed salt solution, bacterium solution and mixed liquor volume ratio are 1:9, shake
It swings uniformly, in 20 DEG C of standing 72h；
Step 5: ultrasonication 30min~1h at 20~40 DEG C obtains suspension；
Step 6: suspension being poured into centrifuge tube, after 4000rpm centrifugation, supernatant liquor is outwelled, deionized water water is added
It washes；
Step 7: repeating step 5,6 three times, wash unreacted water calcium acetate；
Step 8: the white particle sediment after centrifugation is placed in 60 DEG C of drying boxes and is dried for 24 hours, obtain it is different composition and
The calcium carbonate of pattern.
Calcium carbonate prepared by the present embodiment 8 passes through XRD as a result, map H as shown in figure 1,2 θ values 25.0 °, 27.3 °,
33.0 °, 44.1 °, 50.3 ° there are the diffraction maximums of vaterite crystal form feature, contain 100% vaterite-type calcium carbonate；By red
In outer map, map H in Fig. 2, in 745cm-1And 872cm-1There is the absorption peak of vaterite at place.It is observed by SEM, such as Fig. 3
(h) granule-morphology in is spherical shape, and particle size is less than 10 μm.
Using the method for the present invention can by increase calcium ion concentration realize calcium carbonate by single calcite component by
Single vaterite component is crossfaded into, and reaction speed is fast, simple process, agents useful for same is environmental-friendly.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (3)
1. a kind of method using calcium source concentration control calcite and vaterite phase co-conversion, which is characterized in that including following step
It is rapid:
S10: Pasteur's sporosarcina (S.pasteurii) is inoculated on culture medium, and at 30 DEG C, the oscillation of 100r/min is trained
It supports in case and cultivates 48h, obtain bacterium solution；
S20: configuration urea and a water calcium acetate mixed solution be nutrient salt solution, wherein urea concentration be 0.5mol/L, one
Water calcium acetate concentration range is 0.025mol/L~1mol/L；
S30: configuration 0.2g/L urase solution, urease activity are 92~137u/mg, and urase solution is added in nutrient salt solution,
Nutrient salt solution and urase liquor capacity ratio are 8~9:1；
S40: bacterium solution is added in urase and nutrition mixed salt solution, and bacterium solution and mixed liquor volume ratio are 1:9~10, concussion
Uniformly, 72h is stood at 10~30 DEG C；
S50: ultrasonication 30min~1h at 20~40 DEG C, obtain suspension；
S60: suspension is poured into centrifuge tube, after 4000rpm centrifugation, outwells supernatant liquor, and deionized water washing is added；
S70: it repeats step S50 and step S60 three times, washes unreacted water calcium acetate；
S80: the white particle sediment after centrifugation being placed in 60 DEG C of drying boxes and is dried for 24 hours, obtains different compositions and pattern
Calcium carbonate.
2. as described in claim 1 using the method for calcium source concentration control calcite and vaterite phase co-conversion, feature exists
In the composition of the culture medium in the step 1 includes: 10~30g/L of yeast extract, ammonium sulfate 15g/L, and the pH of culture medium is
7~9.5.
3. as described in claim 1 using the method for calcium source concentration control calcite and vaterite phase co-conversion, feature exists
In as a water acetic acid calcium concentration≤0.025mol/L, the calcium carbonate granule of acquisition is single rhombohedron shape calcite；
As a water acetic acid calcium concentration >=1mol/L, the calcium carbonate granule of acquisition is single spherical vaterite；
When a water acetic acid calcium concentration therebetween when, the calcium carbonate granule of acquisition is the mixture of calcite and vaterite,
Particle shape looks are rhombohedron shape, three kinds of spherical shape, spindle-type patterns coexist.
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| CN110615459A (en) * | 2019-10-12 | 2019-12-27 | 辽宁工程技术大学 | Method for preparing spherical vaterite particles by microwave biomineralization |
| CN112794732A (en) * | 2021-01-05 | 2021-05-14 | 中国科学院上海硅酸盐研究所 | Calcium silicate ceramic with surface modified by microbial mineralization and application thereof |
| WO2023216674A1 (en) * | 2022-05-10 | 2023-11-16 | 江苏大学 | Porous biological calcium carbonate-based passivation material with urease activity, method for preparing same, and use thereof |
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| CN110615459A (en) * | 2019-10-12 | 2019-12-27 | 辽宁工程技术大学 | Method for preparing spherical vaterite particles by microwave biomineralization |
| CN110615459B (en) * | 2019-10-12 | 2021-12-10 | 辽宁工程技术大学 | Method for preparing spherical vaterite particles by microwave biomineralization |
| CN112794732A (en) * | 2021-01-05 | 2021-05-14 | 中国科学院上海硅酸盐研究所 | Calcium silicate ceramic with surface modified by microbial mineralization and application thereof |
| CN112794732B (en) * | 2021-01-05 | 2022-04-08 | 中国科学院上海硅酸盐研究所 | Calcium silicate ceramic with surface modified by microbial mineralization and application thereof |
| WO2023216674A1 (en) * | 2022-05-10 | 2023-11-16 | 江苏大学 | Porous biological calcium carbonate-based passivation material with urease activity, method for preparing same, and use thereof |
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Effective date of registration: 20221028 Address after: 116000 Songmudao Chemical Park, Puwan New District, Dalian City, Liaoning Province Patentee after: DALIAN ZION TECHNOLOGY CO.,LTD. Address before: Fuxin City, Liaoning Province, China Road 123000 Xihe District No. 47 Patentee before: LIAONING TECHNICAL University |