CN110156060B - Method for controlling mutual transformation of calcite and vaterite by using calcium source concentration - Google Patents

Method for controlling mutual transformation of calcite and vaterite by using calcium source concentration Download PDF

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CN110156060B
CN110156060B CN201910411312.4A CN201910411312A CN110156060B CN 110156060 B CN110156060 B CN 110156060B CN 201910411312 A CN201910411312 A CN 201910411312A CN 110156060 B CN110156060 B CN 110156060B
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vaterite
calcite
concentration
urease
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CN110156060A (en
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杨建林
张岩
李喜林
王来贵
宋诗雨
陈伟
胡子游
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Dalian Zion Technology Co ltd
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Liaoning Technical University
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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
    • 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
    • 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
    • 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

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Abstract

The invention discloses a method for controlling the interconversion of calcite and vaterite by using the concentration of a calcium source, which comprises the following steps: inoculating sarcina pasteurii (s. pasteurii) on the medium; preparing a nutrient salt solution of urea and calcium acetate monohydrate; preparing a urease solution, and adding the urease solution into a nutrient salt solution; adding the bacterial liquid into a mixed solution of urease and nutrient salt; performing ultrasonic treatment at 20-40 ℃ for 30 min-1 h to obtain a suspension; pouring the suspension into a centrifuge tube, centrifuging at 4000rpm, pouring out supernatant liquid, and adding deionized water for washing; washing away the unreacted calcium acetate monohydrate; and (4) drying the centrifuged white particle precipitate in a drying box to obtain calcium carbonate with different compositions and appearances. The method only changes the concentration of the calcium source, realizes the continuous conversion of the calcium carbonate from a calcite structure to a vaterite structure, and has the advantages of low requirement on environmental conditions, environment-friendly other reagents and high repeatability of experimental results, wherein the calcite and the vaterite coexist in a certain range of the concentration of the calcium source.

Description

Method for controlling mutual transformation of calcite and vaterite by using calcium source concentration
Technical Field
The invention belongs to the technical field of bionic materials, and particularly relates to a method for controlling the mutual transformation of calcite and vaterite by using the concentration of a calcium source.
Background
Calcium carbonate is one of the most common biomineralization materials in nature and is an important component of animal bones, shells, corals, and the like. Calcium carbonate is widely applied in industry, is an important inorganic industrial additive, and can improve the properties of products such as bulkiness, glossiness, brightness, fluidity, strength and the like in the fields of food, paper making, coating, rubber and the like.
Calcium carbonate has many structures and can be classified into anhydrous calcium carbonate and hydrous calcium carbonate depending on whether crystal water is contained or not. The anhydrous calcium carbonate crystals have three crystal forms: calcite, aragonite and vaterite. The calcium carbonate with different crystal forms has larger difference of physical and mechanical properties, and compared with calcite, the vaterite has the advantages of large specific surface area, small specific gravity, good biocompatibility and the like. In the process of repairing concrete cracks and rock-soil cultural relic cracks by using microorganism-induced calcium carbonate, the vaterite has higher fluidity and filling property than calcite, and can form composite gel with hydrated calcium silicate which is a hydration product of cement, so that the strength and durability of the concrete are obviously improved. Vaterite belongs to a metastable phase, and in a humid environment, the vaterite can be converted into calcite in a short time, so that the mechanical strength of repairing cracks is further improved. Therefore, by changing the relative content of the calcite and the vaterite, the fluidity, the filling rate and the mechanical strength of the slurry can be adjusted, so that the repairing effect of concrete cracks and rock and soil cultural relic cracks is obviously improved. There is a need to develop a method for controlling the conversion of calcite to vaterite, which can continuously control the contents of calcite and vaterite.
In the existing documents or patents, additives such as surfactants and organic macromolecules are mostly added to obtain the vaterite micro-nano particles with single morphology. At present, no report is made on a method for controlling the interconversion between calcite and vaterite by using the calcium source concentration.
Disclosure of Invention
Based on the defects of the prior art, the technical problem solved by the invention is to provide a method for controlling the mutual transformation of calcite and vaterite by using the concentration of a calcium source, and obtain a method capable of continuously regulating the relative content and morphology of the calcite and the vaterite.
In order to solve the technical problems, the invention is realized by the following technical scheme: the invention provides a method for controlling the interconversion of calcite and vaterite by using the concentration of a calcium source, which comprises the following steps:
s10: inoculating Sporosarcina pasteurii (S.pasteurii) on a culture medium, and culturing for 48h in a shaking culture box at 30 ℃ and 100r/min to obtain a bacterial liquid;
s20: preparing a mixed solution of urea and calcium acetate monohydrate as a nutrient salt solution, wherein the concentration of the urea is 0.5mol/L, and the concentration range of the calcium acetate monohydrate is 0.025 mol/L-1 mol/L;
s30: preparing 0.2g/L urease solution, wherein the activity of urease is 92-137 u/mg, and adding the urease solution into a nutrient salt solution, wherein the volume ratio of the nutrient salt solution to the urease solution is 8-9: 1;
s40: adding the bacterial liquid into a mixed solution of urease and nutrient salt, wherein the volume ratio of the bacterial liquid to the mixed solution is 1: 9-10, shaking uniformly, and standing for 72 hours at 10-30 ℃;
s50: performing ultrasonic treatment at 20-40 ℃ for 30 min-1 h to obtain a suspension;
s60: pouring the suspension into a centrifuge tube, centrifuging at 4000rpm, pouring out supernatant liquid, and adding deionized water for washing;
s70: repeating the steps S50 and S60 three times, and washing away unreacted calcium acetate monohydrate;
s80: and (3) drying the white particle precipitate after centrifugation in a drying box at 60 ℃ for 24h to obtain calcium carbonate with different compositions and appearances.
Preferably, the composition of the culture medium in step 1 comprises: 10-30 g/L of yeast extract, 15g/L of ammonium sulfate and the pH value of the culture medium is 7-9.5.
Further, when the concentration of the calcium acetate monohydrate is less than or equal to 0.025mol/L, the obtained calcium carbonate particles are single rhombohedral calcite;
when the concentration of the calcium acetate monohydrate is more than or equal to 1mol/L, the obtained calcium carbonate particles are single spherical vaterite;
when the concentration of the calcium acetate monohydrate is between the two, the obtained calcium carbonate particles are a mixture of calcite and vaterite, and the particle morphology is a rhombohedral morphology, a spherical morphology and a spindle morphology.
From the above, the method for controlling the interconversion between calcite and vaterite by using the calcium source concentration has at least the following beneficial effects:
1. the continuous conversion of calcium carbonate from a calcite structure to a vaterite structure is realized only by changing the concentration of the calcium source, the crystal structure of the calcium carbonate is single calcite when the concentration of the calcium source is low, and the crystal structure of the calcium carbonate is single vaterite when the concentration of the calcium source is high.
2. In a certain range of calcium source concentration, calcite and vaterite coexist, three morphology particles of rhombohedral shape, spherical shape and spindle shape coexist, the formed whole is more compact, and the mechanical strength of the calcium carbonate is higher than that of calcium carbonate with a single component. Lays a foundation for the application of the microbial mortar in the concrete crack repair and the stone cultural relic crack repair.
3. Meanwhile, urease-producing microorganisms and urease are used, the urease-producing microorganisms are favorable for nucleation of crystals, and substances such as urease and a calcium source and the like form a large amount of calcite and vaterite in a short time, so that the cracks can be quickly filled, the urease-producing microorganisms still have activity after a long time, can further fill the pores and the cracks, and are more suitable for repairing concrete cracks and stone cultural relic cracks.
4. The microorganisms used in the invention are microorganisms widely distributed in soil, the requirement on environmental conditions is low, other reagents used are environment-friendly, the reaction speed is high, the process is simple, and the repeatability of experimental results is high.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with the preferred embodiments, together with the accompanying drawings.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is XRD spectrograms of calcium carbonate samples with different morphologies prepared in examples 1 to 8 of the present invention, wherein the diffraction line A, B, C, D in (a) respectively corresponds to the XRD spectrograms of the samples obtained in examples 1, 2, 3 and 4; (b) the middle E, F, G, H diffraction line corresponds to the XRD spectra of the samples obtained in examples 5, 6, 7 and 8 respectively;
FIG. 2 is an infrared spectrogram of calcium carbonate samples with different morphologies prepared in examples 1 to 8, wherein the A, B, C, D diffraction line in (a) corresponds to the infrared spectrogram of the samples obtained in examples 1, 2, 3 and 4, respectively; (b) the middle E, F, G, H diffraction line corresponds to the infrared spectra of the samples obtained in examples 5, 6, 7 and 8 respectively;
FIG. 3 is SEM pictures of calcium carbonate samples with different morphologies prepared in examples 1-8 of the present invention, wherein the images (a), (b), (c), (d), (e), (f), (g) and (h) are SEM pictures of calcium carbonate prepared in examples 1, 2, 3, 4, 5, 6, 7 and 8, respectively;
figure 4 is a flow diagram of the method of the present invention for controlling the interconversion of calcite and vaterite using calcium source concentration.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which form a part of this specification, and which illustrate, by way of example, the principles of the invention. In the referenced drawings, the same or similar components in different drawings are denoted by the same reference numerals.
The sporosarcina pasteurii adopted in the embodiment of the invention is from American type culture Collection and is numbered as ATCC 11859. Sporosarcina pasteurii is gram-positive, oval rod-shaped in appearance, with spores and without capsules. The bacteria can grow at the temperature of 4-37 ℃ and the pH value of 7-9.5.
The urea is produced by Michelin company and has a molecular formula of CH4N2O, analytically pure, purity 99%.
The calcium acetate monohydrate is produced by Michelin company and has a molecular formula of C4H8CaO5Analytically pure, purity 98%.
The urease used was produced by TOYOBO of Japan, and the activity was 148 u/mg.
The yeast extract is produced by Shanghai Bo microbial science and technology limited, the total nitrogen is 11.57%, the drying weight loss is 4.8%, the ash content is 9.5%, the chloride is less than 6%, and the pH value is 6.8 (2% solution).
The ammonium sulfate is produced by national medicine group chemical reagent limited company and has the molecular formula of (NH)4)2SO4Analytically pure, purity 99%.
According to the method for controlling the mutual conversion between the calcite and the vaterite by utilizing the calcium source concentration, the composition components of the sample are the vaterite and the calcite, and the content range of the vaterite is 0-100%.
The invention utilizes the concentration of a calcium source to control the mutual transformation of calcite and vaterite, when the concentration of calcium acetate monohydrate is less than or equal to 0.025mol/L, the content of the vaterite is 0 percent, the content of the calcite is 100 percent, the shape of the formed particles is rhombohedral, and the size is less than 15 mu m; when the concentration of the calcium acetate monohydrate is between 0.025mol/L and 1mol/L, the content of the vaterite is continuously changed between 0 percent and 100 percent, the morphology of the composition particles is in a coexistence of a rhombohedral shape and a spherical shape, and the size is less than 25 mu m; when the concentration of the calcium acetate monohydrate is more than or equal to 1mol/L, the content of the vaterite is 100 percent, the content of the calcite is 0 percent, the shape of the formed particles is spherical, and the size of the particles is less than 10 mu m.
The present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
Example 1
Step 1: inoculating Sporosarcina pasteurii (S.pasteurii) on a culture medium, and culturing for 48h in a shaking culture box at 30 ℃ and 100r/min to obtain a bacterial liquid; wherein the culture medium comprises 10-30 g/L of yeast extract and 15g/L of ammonium sulfate, and the pH value of the culture medium is 7-9.5;
step 2: preparing a mixed solution of urea and calcium acetate monohydrate as a nutrient salt solution, wherein the concentration of the urea is 0.5mol/L, and the concentration of the calcium acetate monohydrate is 0.025 mol/L;
and step 3: preparing 0.2g/L urease solution (the activity of the urease is 137u/mg), adding the urease solution into a nutrient salt solution, wherein the volume ratio of the nutrient salt solution to the urease solution is 9: 1;
and 4, step 4: adding the bacterial liquid into a mixed solution of urease and nutrient salt, wherein the volume ratio of the bacterial liquid to the mixed solution is 1:10, shaking uniformly, and standing for 72 hours at 20 ℃;
and 5: performing ultrasonic treatment at 20-40 ℃ for 30 min-1 h to obtain a suspension;
step 6: pouring the suspension into a centrifuge tube, centrifuging at 4000rpm, pouring out supernatant liquid, and adding deionized water for washing;
and 7: repeating the steps 5 and 6 for three times, and washing away unreacted calcium acetate monohydrate;
and 8: and (3) drying the white particle precipitate after centrifugation in a drying box at 60 ℃ for 24h to obtain calcium carbonate with different compositions and appearances.
According to the XRD result of the calcium carbonate prepared in the example 1, as shown in a graph A in figure 1, characteristic diffraction peaks of calcite crystal forms exist at the 2 theta values of 23.3 degrees, 29.7 degrees, 36.3 degrees, 39.8 degrees, 43.5 degrees, 47.8 degrees and 48.9 degrees, and the sample contains 100% of calcite calcium carbonate; by means of infrared spectroscopy, it can also be observed at 712cm in the spectrum A in FIG. 2-1And 876cm-1Has a characteristic absorption peak of-C-O-C-. By SEM observation, as shown in FIG. 3 (a), the morphology of the particles was rhombohedral, and the particle size was less than 15 μm.
Example 2
Step 1: inoculating Sporosarcina pasteurii (S.pasteurii) on a culture medium, and culturing for 48h in a shaking culture box at 30 ℃ and 100r/min to obtain a bacterial liquid; wherein the culture medium comprises 10-30 g/L of yeast extract and 15g/L of ammonium sulfate, and the pH value of the culture medium is 7-9.5;
step 2: preparing a mixed solution of urea and calcium acetate monohydrate as a nutrient salt solution, wherein the concentration of the urea is 0.5mol/L, and the concentration of the calcium acetate monohydrate is 0.1 mol/L;
and step 3: preparing 0.2g/L urease solution (the activity of the urease is 137u/mg), adding the urease solution into a nutrient salt solution, wherein the volume ratio of the nutrient salt solution to the urease solution is 8: 1;
and 4, step 4: adding the bacterial liquid into a mixed solution of urease and nutrient salt, wherein the volume ratio of the bacterial liquid to the mixed solution is 1:10, shaking uniformly, and standing for 72 hours at 20 ℃;
and 5: performing ultrasonic treatment at 20-40 ℃ for 30 min-1 h to obtain a suspension;
step 6: pouring the suspension into a centrifuge tube, centrifuging at 4000rpm, pouring out supernatant liquid, and adding deionized water for washing;
and 7: repeating the steps 5 and 6 for three times, and washing away unreacted calcium acetate monohydrate;
and 8: and (3) drying the white particle precipitate after centrifugation in a drying box at 60 ℃ for 24h to obtain calcium carbonate with different compositions and appearances.
As a result of XRD, the calcium carbonate prepared in this example 2 has characteristic diffraction peaks of calcite crystal form at 2 θ values of 23.3 °, 29.7 °, 36.3 °, 39.8 °, 43.5 °, 47.8 ° and 48.9 ° while diffraction peaks of vaterite crystal form at 2 θ values of 25.0 °, 27.3 °, 33.0 °, 44.1 ° and 50.3 ° as shown in pattern B of fig. 1, and contains 82% of calcite-type calcium carbonate and 18% of vaterite-type calcium carbonate; from the infrared spectrum, spectrum B in FIG. 2, a spectrum at 712cm was also observed-1And 876cm-1Has calcite absorption peak at 745cm-1And 872cm-1There is an absorption peak of vaterite. The morphology of the particles as shown in FIG. 3(b) was observed by SEM to be a mixture of rhombohedral and spherical morphologies, and the particle size was less than 20 μm.
Example 3
Step 1: inoculating Sporosarcina pasteurii (S.pasteurii) on a culture medium, and culturing for 48h in a shaking culture box at 30 ℃ and 100r/min to obtain a bacterial liquid; wherein the culture medium comprises 10-30 g/L of yeast extract and 15g/L of ammonium sulfate, and the pH value of the culture medium is 7-9.5;
step 2: preparing a mixed solution of urea and calcium acetate monohydrate as a nutrient salt solution, wherein the concentration of the urea is 0.5mol/L, and the concentration of the calcium acetate monohydrate is 0.3 mol/L;
and step 3: preparing 0.2g/L urease solution (the activity of the urease is 110u/mg), and adding the urease solution into a nutrient salt solution, wherein the volume ratio of the nutrient salt solution to the urease solution is 9: 1;
and 4, step 4: adding the bacterial liquid into a mixed solution of urease and nutrient salt, wherein the volume ratio of the bacterial liquid to the mixed solution is 1:10, shaking uniformly, and standing at 10 ℃ for 72 hours;
and 5: performing ultrasonic treatment at 20-40 ℃ for 30 min-1 h to obtain a suspension;
step 6: pouring the suspension into a centrifuge tube, centrifuging at 4000rpm, pouring out supernatant liquid, and adding deionized water for washing;
and 7: repeating the steps 5 and 6 for three times, and washing away unreacted calcium acetate monohydrate;
and 8: and (3) drying the white particle precipitate after centrifugation in a drying box at 60 ℃ for 24h to obtain calcium carbonate with different compositions and appearances.
As a result of XRD, the calcium carbonate prepared in this example 3 has diffraction peaks with calcite crystal form characteristics at 2 θ values of 23.3 °, 29.7 °, 36.3 °, 39.8 °, 43.5 °, 47.8 ° and 48.9 ° while diffraction peaks with vaterite crystal form characteristics at 2 θ values of 25.0 °, 27.3 °, 33.0 °, 44.1 ° and 50.3 ° as shown in pattern C in fig. 1, and contains 56% of calcite-type calcium carbonate and 44% of vaterite-type calcium carbonate; from the infrared spectrum, spectrum C in FIG. 2, it can also be observed at 712cm-1And 876cm-1Has calcite absorption peak at 745cm-1And 872cm-1There is an absorption peak of vaterite. The morphology of the particles as shown in FIG. 3(c) was observed by SEM to be coexistence of rhombohedral and spherical morphologies, and the particle size was less than 25 μm.
Example 4
Step 1: inoculating Sporosarcina pasteurii (S.pasteurii) on a culture medium, and culturing for 48h in a shaking culture box at 30 ℃ and 100r/min to obtain a bacterial liquid; wherein the culture medium comprises 10-30 g/L of yeast extract and 15g/L of ammonium sulfate, and the pH value of the culture medium is 7-9.5;
step 2: preparing a mixed solution of urea and calcium acetate monohydrate as a nutrient salt solution, wherein the concentration of the urea is 0.5mol/L, and the concentration of the calcium acetate monohydrate is 0.5 mol/L;
and step 3: preparing 0.2g/L urease solution (the activity of the urease is 100u/mg), and adding the urease solution into a nutrient salt solution, wherein the volume ratio of the nutrient salt solution to the urease solution is 9: 1;
and 4, step 4: adding the bacterial liquid into a mixed solution of urease and nutrient salt, wherein the volume ratio of the bacterial liquid to the mixed solution is 1:9, shaking uniformly, and standing for 72 hours at 20 ℃;
and 5: performing ultrasonic treatment at 20-40 ℃ for 30 min-1 h to obtain a suspension;
step 6: pouring the suspension into a centrifuge tube, centrifuging at 4000rpm, pouring out supernatant liquid, and adding deionized water for washing;
and 7: repeating the steps 5 and 6 for three times, and washing away unreacted calcium acetate monohydrate;
and 8: and (3) drying the white particle precipitate after centrifugation in a drying box at 60 ℃ for 24h to obtain calcium carbonate with different compositions and appearances.
As a result of XRD, the calcium carbonate prepared in this example 4 has diffraction peaks with calcite crystal form characteristics at 2 θ values of 23.3 °, 29.7 °, 36.3 °, 39.8 °, 43.5 °, 47.8 ° and 48.9 ° while diffraction peaks with vaterite crystal form characteristics at 2 θ values of 25.0 °, 27.3 °, 33.0 °, 44.1 ° and 50.3 ° as shown in pattern D in fig. 1, and contains 50% of calcite-type calcium carbonate and 50% of vaterite-type calcium carbonate; from the infrared spectrum, spectrum D in FIG. 2, at 712cm, can also be observed-1And 876cm-1Has calcite absorption peak at 745cm-1And 872cm-1There is an absorption peak of vaterite. The morphology of the particles as shown in FIG. 3(d) was observed by SEM to be coexistence of rhombohedral and spherical morphologies, and the particle size was less than 25 μm.
Example 5
Step 1: inoculating Sporosarcina pasteurii (S.pasteurii) on a culture medium, and culturing for 48h in a shaking culture box at 30 ℃ and 100r/min to obtain a bacterial liquid; wherein the culture medium comprises 10-30 g/L of yeast extract and 15g/L of ammonium sulfate, and the pH value of the culture medium is 7-9.5;
step 2: preparing a mixed solution of urea and calcium acetate monohydrate as a nutrient salt solution, wherein the concentration of the urea is 0.5mol/L, and the concentration of the calcium acetate monohydrate is 0.6 mol/L;
and step 3: preparing 0.2g/L urease solution (the activity of the urease is 120u/mg), and adding the urease solution into a nutrient salt solution, wherein the volume ratio of the nutrient salt solution to the urease solution is 8: 1;
and 4, step 4: adding the bacterial liquid into a mixed solution of urease and nutrient salt, wherein the volume ratio of the bacterial liquid to the mixed solution is 1:10, shaking uniformly, and standing for 72 hours at 30 ℃;
and 5: performing ultrasonic treatment at 20-40 ℃ for 30 min-1 h to obtain a suspension;
step 6: pouring the suspension into a centrifuge tube, centrifuging at 4000rpm, pouring out supernatant liquid, and adding deionized water for washing;
and 7: repeating the steps 5 and 6 for three times, and washing away unreacted calcium acetate monohydrate;
and 8: and (3) drying the white particle precipitate after centrifugation in a drying box at 60 ℃ for 24h to obtain calcium carbonate with different compositions and appearances.
As a result of XRD, the calcium carbonate prepared in this example 5 has diffraction peaks with calcite crystal form characteristics at 2 θ values of 23.3 °, 29.7 °, 36.3 °, 39.8 °, 43.5 °, 47.8 ° and 48.9 ° while diffraction peaks with vaterite crystal form characteristics at 2 θ values of 25.0 °, 27.3 °, 33.0 °, 44.1 ° and 50.3 ° as shown in pattern E in fig. 1, and contains 33% of calcite-type calcium carbonate and 67% of vaterite-type calcium carbonate; in the infrared spectrum, a spectrum at 712cm can also be observed-1And 876cm-1Has calcite absorption peak at 745cm-1And 872cm-1There is a absorption peak of vaterite, as shown in graph E of fig. 2. Through SEM observation, the particle morphology shown in FIG. 3(e) is the coexistence of three morphologies, namely rhombohedral morphology, spherical morphology and spindle morphology, and the particle size is less than 20 μm.
Example 6
Step 1: inoculating Sporosarcina pasteurii (S.pasteurii) on a culture medium, and culturing for 48h in a shaking culture box at 30 ℃ and 100r/min to obtain a bacterial liquid; wherein the culture medium comprises 10-30 g/L of yeast extract and 15g/L of ammonium sulfate, and the pH value of the culture medium is 7-9.5;
step 2: preparing a mixed solution of urea and calcium acetate monohydrate as a nutrient salt solution, wherein the concentration of the urea is 0.5mol/L, and the concentration of the calcium acetate monohydrate is 0.8 mol/L;
and step 3: preparing 0.2g/L urease solution (the activity of the urease is 130u/mg), and adding the urease solution into a nutrient salt solution, wherein the volume ratio of the nutrient salt solution to the urease solution is 9: 1;
and 4, step 4: adding the bacterial liquid into a mixed solution of urease and nutrient salt, wherein the volume ratio of the bacterial liquid to the mixed solution is 1:10, shaking uniformly, and standing at 10 ℃ for 72 hours;
and 5: performing ultrasonic treatment at 20-40 ℃ for 30 min-1 h to obtain a suspension;
step 6: pouring the suspension into a centrifuge tube, centrifuging at 4000rpm, pouring out supernatant liquid, and adding deionized water for washing;
and 7: repeating the steps 5 and 6 for three times, and washing away unreacted calcium acetate monohydrate;
and 8: and (3) drying the white particle precipitate after centrifugation in a drying box at 60 ℃ for 24h to obtain calcium carbonate with different compositions and appearances.
As a result of XRD, the calcium carbonate prepared in this example 6 has diffraction peaks with calcite crystal form characteristics at 2 θ values of 23.3 °, 29.7 °, 36.3 °, 39.8 °, 43.5 °, 47.8 ° and 48.9 ° while diffraction peaks with vaterite crystal form characteristics at 2 θ values of 25.0 °, 27.3 °, 33.0 °, 44.1 ° and 50.3 ° as shown in pattern F in fig. 1, and contains 29% of calcite-type calcium carbonate and 71% of vaterite-type calcium carbonate; from the infrared spectrum, spectrum F in FIG. 2, a spectrum at 712cm can also be observed-1And 876cm-1Has calcite absorption peak at 745cm-1And 872cm-1There is an absorption peak of vaterite. Through SEM observation, the particle morphology shown in FIG. 3(f) is the coexistence of three morphologies, namely rhombohedral morphology, spherical morphology and spindle morphology, and the particle size is less than 20 μm.
Example 7
Step 1: inoculating Sporosarcina pasteurii (S.pasteurii) on a culture medium, and culturing for 48h in a shaking culture box at 30 ℃ and 100r/min to obtain a bacterial liquid; wherein the culture medium comprises 10-30 g/L of yeast extract and 15g/L of ammonium sulfate, and the pH value of the culture medium is 7-9.5;
step 2: preparing a mixed solution of urea and calcium acetate monohydrate as a nutrient salt solution, wherein the concentration of the urea is 0.5mol/L, and the concentration of the calcium acetate monohydrate is 0.9 mol/L;
and step 3: preparing 0.2g/L urease solution (the activity of the urease is 92u/mg), and adding the urease solution into a nutrient salt solution, wherein the volume ratio of the nutrient salt solution to the urease solution is 9: 1;
and 4, step 4: adding the bacterial liquid into a mixed solution of urease and nutrient salt, wherein the volume ratio of the bacterial liquid to the mixed solution is 1:10, shaking uniformly, and standing for 72 hours at 20 ℃;
and 5: performing ultrasonic treatment at 20-40 ℃ for 30 min-1 h to obtain a suspension;
step 6: pouring the suspension into a centrifuge tube, centrifuging at 4000rpm, pouring out supernatant liquid, and adding deionized water for washing;
and 7: repeating the steps 5 and 6 for three times, and washing away unreacted calcium acetate monohydrate;
and 8: and (3) drying the white particle precipitate after centrifugation in a drying box at 60 ℃ for 24h to obtain calcium carbonate with different compositions and appearances.
As a result of XRD, the calcium carbonate prepared in this example 7 has diffraction peaks with calcite crystal form characteristics at 2 θ values of 23.3 °, 29.7 °, 36.3 °, 39.8 °, 43.5 °, 47.8 ° and 48.9 ° while diffraction peaks with vaterite crystal form characteristics at 2 θ values of 25.0 °, 27.3 °, 33.0 °, 44.1 ° and 50.3 ° as shown in pattern G in fig. 1, and contains 16% of calcite-type calcium carbonate and 84% of vaterite-type calcium carbonate; from the infrared spectrum, spectrum G in FIG. 2, at 712cm, can also be observed-1And 876cm-1Has calcite absorption peak at 745cm-1And 872cm-1There is an absorption peak of vaterite. Through SEM observation, the particle morphology shown in FIG. 3(g) is the coexistence of three morphologies, namely rhombohedral morphology, spherical morphology and spindle morphology, and the particle size is less than 20 μm.
Example 8
Step 1: inoculating Sporosarcina pasteurii (S.pasteurii) on a culture medium, and culturing for 48h in a shaking culture box at 30 ℃ and 100r/min to obtain a bacterial liquid; wherein the culture medium comprises 10-30 g/L of yeast extract and 15g/L of ammonium sulfate, and the pH value of the culture medium is 7-9.5;
step 2: preparing a mixed solution of urea and calcium acetate monohydrate as a nutrient salt solution, wherein the concentration of the urea is 0.5mol/L, and the concentration of the calcium acetate monohydrate is 1 mol/L;
and step 3: preparing 0.2g/L urease solution (the activity of the urease is 137u/mg), adding the urease solution into a nutrient salt solution, wherein the volume ratio of the nutrient salt solution to the urease solution is 8: 1;
and 4, step 4: adding the bacterial liquid into a mixed solution of urease and nutrient salt, wherein the volume ratio of the bacterial liquid to the mixed solution is 1:9, shaking uniformly, and standing for 72 hours at 20 ℃;
and 5: performing ultrasonic treatment at 20-40 ℃ for 30 min-1 h to obtain a suspension;
step 6: pouring the suspension into a centrifuge tube, centrifuging at 4000rpm, pouring out supernatant liquid, and adding deionized water for washing;
and 7: repeating the steps 5 and 6 for three times, and washing away unreacted calcium acetate monohydrate;
and 8: and (3) drying the white particle precipitate after centrifugation in a drying box at 60 ℃ for 24h to obtain calcium carbonate with different compositions and appearances.
The calcium carbonate prepared in this example 8 was subjected to XRD results, as shown in fig. 1, pattern H, with diffraction peaks having vaterite crystal form characteristics at 25.0 °, 27.3 °, 33.0 °, 44.1 °, and 50.3 ° 2 θ values, containing 100% vaterite-type calcium carbonate; by infrared spectrum, spectrum H in figure 2, at 745cm-1And 872cm-1There is an absorption peak of vaterite. The morphology of the particles as in FIG. 3(h) was spherical and the particle size was less than 10 μm as observed by SEM.
The method can realize that the calcium carbonate is gradually changed into a single vaterite component from a single calcite component by increasing the concentration of calcium ions, and has the advantages of high reaction speed, simple process and environment-friendly used reagents.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims (2)

1. A method for controlling the interconversion of calcite and vaterite using the concentration of a calcium source, comprising the steps of:
s10: inoculating Sporosarcina pasteurii on a culture medium, and culturing for 48h in a shaking culture box at 30 ℃ and 100r/min to obtain a bacterial liquid;
s20: preparing a mixed solution of urea and calcium acetate monohydrate as a nutrient salt solution, wherein the concentration of the urea is 0.5mol/L, and the concentration range of the calcium acetate monohydrate is 0.025 mol/L-1 mol/L;
s30: preparing 0.2g/L urease solution, wherein the activity of urease is 92-137 u/mg, and adding the urease solution into a nutrient salt solution, wherein the volume ratio of the nutrient salt solution to the urease solution is 8-9: 1;
s40: adding the bacterial liquid into a mixed solution of urease and nutrient salt, wherein the volume ratio of the bacterial liquid to the mixed solution is 1: 9-10, shaking uniformly, and standing for 72 hours at 10-30 ℃;
s50: performing ultrasonic treatment at 20-40 ℃ for 30 min-1 h to obtain a suspension;
s60: pouring the suspension into a centrifuge tube, centrifuging at 4000rpm, pouring out supernatant liquid, and adding deionized water for washing;
s70: repeating the steps S50 and S60 three times, and washing away unreacted calcium acetate monohydrate;
s80: drying the white particle precipitate after centrifugation in a drying oven at 60 ℃ for 24h to obtain calcium carbonate with different compositions and appearances;
when the concentration of calcium acetate monohydrate is 0.025mol/L, the obtained calcium carbonate particles are single rhombohedral calcite;
when the concentration of calcium acetate monohydrate is 1mol/L, the obtained calcium carbonate particles are single spherical vaterite;
when the concentration of the calcium acetate monohydrate is 0.6-0.9mol/L, the obtained calcium carbonate particles are a mixture of calcite and vaterite, and the particle morphology is rhombohedral morphology, spherical morphology and spindle morphology.
2. The method for controlling the interconversion of calcite and vaterite using the calcium source concentration according to claim 1, wherein the composition of the medium in step S10 comprises: 10-30 g/L of yeast extract, 15g/L of ammonium sulfate and the pH value of the culture medium is 7-9.5.
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