CN100357444C - Preparation of calcium carbonate by microbe deposition - Google Patents

Preparation of calcium carbonate by microbe deposition Download PDF

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CN100357444C
CN100357444C CNB2005100947445A CN200510094744A CN100357444C CN 100357444 C CN100357444 C CN 100357444C CN B2005100947445 A CNB2005100947445 A CN B2005100947445A CN 200510094744 A CN200510094744 A CN 200510094744A CN 100357444 C CN100357444 C CN 100357444C
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lime carbonate
deposition
calcium carbonate
solution
bacterium liquid
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CN1778934A (en
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钱春香
王瑞兴
王剑云
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Southeast University
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Abstract

The present invention discloses a method for preparing calcium carbonate by microorganism deposition. Bacterial strains of Bacillus pasteurii are inoculated to a culture medium containing urea substrate to be in shake cultivation at the temperature of 25 to 37 DEG C, initial pH value is regulated and controlled between 6.0 to 8.0 for the cultivation for 12 to 24 hours, bacterium liquid is taken out, CaCl2 solution is incorporated, generated precipitates are taken out, and the precipitate are filtered and dried to obtain calcium carbonate. The present invention has the advantages of abound resources, simple technology, clean environment, low cost, high purity of prepared calcium carbonate by deposition, high production rate, etc. The present invention can fully utilize microorganism resources in the natural world, be used as fillings, be used for repairing building cracks, and be used as cementing of reclaimed concrete.

Description

Utilize microbe deposition to prepare the method for lime carbonate
Technical field
The present invention relates to a kind of preparation method of lime carbonate, especially a kind of method of utilizing microbe deposition to prepare lime carbonate.
Background technology
Lime carbonate is a kind of important inorganic chemical product, is widely used in industries such as rubber, plastics, printing ink, papermaking, coating, sealing agent, tackiness agent, daily necessities, makeup, food and feed and medicine.At present its preparation technology mainly is divided into mechanical crushing method and chemical reaction method, and positive sternness is faced with that resource is weary frequently, problems such as energy consumption is big, dust is many, product specification is not enough, quality instability in the former production process; And the latter also exists complex process in process of production, and energy consumption is big, the fume emission problem.Therefore, problems such as the resource scarcity that exists in traditional lime carbonate industrial production process, environmental pollution, ecological damage can not be ignored.
Biomineralization is a kind of very general spontaneous phenomenon, and almost each biology can both synthetic mineral.Biomineralization often can form ordered arrangement, that structure is very excellent is natural organic---inorganic composite materials, wherein nearly 2nd/3rd, calcium ore deposit, and quite a few has glued function.They are by the vital movement of himself, and between the surrounding environment medium constantly circulation enzyme is taking place is turning usefulness into, mineralising forms a kind of cementing material gradually---calcite (lime carbonate), pass through the accumulation in very long period again, the most at last the hard rock of the glued formation of the sedimentary loose detrital material of occurring in nature.
Summary of the invention
The invention provides a kind of biological enzyme that utilizes and turn usefulness into, the artificial microbe deposition that utilizes that quickens deposition preparation lime carbonate prepares the method for lime carbonate.
The present invention adopts following technical scheme:
A kind of method of utilizing microbe deposition to prepare lime carbonate, bacterial strain Pasteur bacillus Bacilluspasteurii is seeded to is equipped with on the substratum that contains the urea substrate, under 25~37 ℃, carry out shaking culture, and initial pH is controlled at 6.0~8.0, cultivated 12~24 hours, take out bacterium liquid, mix CaCl 2Solution, last, will produce precipitation and take out, filter, dry, can obtain lime carbonate.
The present invention is seeded to bacterial strain Bacillus pasteurii in the substratum, is nutrition source with the substrate urea in the substratum, produces urase, continuous decomposing urea, cause the suitable rising of pH value in the solution, be more conducive to the growth and breeding of thalline, enzyme turns into also being able to continuous enhancing.In this working cycle, substrate urea constantly decomposes, and makes the CO in the solution 3 2-Concentration constantly increases.In solution, introduce Ca this moment 2+, the continuous immediately chelating Ca of SM (water soluble organic matter) that somatic cells membrane interface place is electronegative 2+, induce partial crystal negatively charged ion (CO 3 2-) concentration further increases, thereby attract more Ca 2+, increase to up to crystal precursor concentration and to be beneficial to coring, deposit CaCO 3Particle, entire reaction is suc as formula shown in 1~formula 3:
The bacterial classification enzymeization
(NH 2) 2CO+2H 2O————→CO 3 2-+2NH 4 + (1)
Cell+Ca 2+=Cell-Ca 2+ (2)
Cell-Ca 2++CO 3 2-=Cell-CaCO 3 (3)
Compared with prior art, the present invention has following advantage:
The present invention makes full use of the nature microorganism resource, by the mineralization of biology, quickens deposition preparation lime carbonate, and not only aboundresources, and technology is simple, and clean environment is with low cost, and the lime carbonate purity height of the preparation that deposits, productive rate are also up to arriving nearly 90%.Room temperature condition can deposit the calcite crystal form calcium carbonate that obtains regular spherical down, not only can be used as filler and uses, and can also be used for the repairing of building tear, the gluing of regeneration concrete etc.; 50 ℃~70 ℃ can deposit the meta crystal formation vaterite that obtains lime carbonate down; Introduce nucleator MgSO 4Behind the solution, and adopt the magnetic alr mode, sedimentary calcium carbonate granule size minimum is refined to about 0.3 μ m.
Description of drawings
Fig. 1 is microbe deposition CaCO under the room temperature 3The X-ray diffraction analysis collection of illustrative plates.
Fig. 2 is microbe deposition CaCO under the room temperature 3Observed granule-morphology under scanning electronic microscope, wherein, (a) CaCO 3Particle overall distribution situation; (b) CaCO of surface attachment thalline 3Particle.
Fig. 3 is microbe deposition CaCO under 50 ℃~70 ℃ conditions of constant temperature 3The X-ray diffraction analysis collection of illustrative plates, wherein, A is a vaterite, B is a calcite.
Fig. 4 is microbe deposition CaCO under 50 ℃~70 ℃ conditions of constant temperature 3Observed granule-morphology under scanning electronic microscope wherein, is spherical, square CaCO3 granule-morphology (calcite) (a), (b) is fusiform CaCO3 granule-morphology (vaterite).
Fig. 5 is nucleator MgSO 4Introduce back microbe deposition CaCO 3The X-ray diffraction analysis collection of illustrative plates.
Fig. 6 is nucleator MgSO 4Introduce back microbe deposition CaCO 3Observed granule-morphology under scanning electronic microscope.
Embodiment
Embodiment 1
A kind of method of utilizing microbe deposition to prepare lime carbonate, bacterial strain Pasteur bacillus Bacilluspasteurii is seeded to is equipped with on the substratum that contains the urea substrate, under 25~37 ℃, carry out shaking culture, and initial pH is controlled at 6.0~8.0, cultivated 12~24 hours, take out bacterium liquid, mix CaCl 2Solution, last, will produce precipitation and take out, filter, dry, can obtain lime carbonate, in the present embodiment, the temperature of shaking culture can be selected 25,30 or 37 ℃, and initial pH is controlled at 6.0,7.0 or 8.0, and incubation time can be selected 12,15,17,20 or 24 hours.In addition, present embodiment can be heated to 50 ℃~70 ℃ (as: 50 ℃, 70 ℃, 55 ℃ or 60 ℃) with the bacterium liquid that takes out, and mixes CaCl under 50 ℃~70 ℃ 2Solution; Present embodiment also can mix CaCl under room temperature after taking out bacterium liquid 2Solution; Present embodiment can also mix the MgSO as nucleator in the bacterium liquid that takes out 4Solution, and adopt magnetic to stir 5~10min, concrete magnetic churning time can select 5,7,9 or 10min for use.The composition of above-mentioned substratum and proportioning are: peptone: meat extract: agar: urea: distilled water=0.005: 0.003: 0.015: 0.01~0.10: 1.
Embodiment 2
Bacterial strain Bacillus pasteurii is seeded to (medium component is as shown in table 1) in the triangular flask that substratum is housed, 25~37 ℃ of shaking culture in the constant-temperature shaking culture case, initial pH condition is controlled at 6.0~8.0, cultivates taking-up in 12~24 hours, mixes CaCl under the normal temperature 2Solution produces precipitation rapidly, with its filtration, oven dry, is calcite type calcium carbonate (Fig. 1) through X-ray diffraction analysis, and purity is very high, and granule-morphology as shown in Figure 2, and is spherical in shape, and particle surface is also adhering to remaining thalline.
Table 1 medium component
Nutritive substance Quality (g) Main effect
Peptone meat extract agar urea distilled water 5.0 3.0 15.0 20.0 1000.0 Nitrogenous source is provided, carbon source (energy), somatomedin provides nitrogenous source, carbon source (energy), inorganic salt, mix strains A enzyme reaction participation substrate during somatomedin preparation solid medium moisture is provided
Embodiment 3
Bacterial strain Bacillus pasteurii is seeded to (medium component is as shown in table 1) in the triangular flask that substratum is housed, 25~37 ℃ of shaking culture in the constant-temperature shaking culture case, initial pH condition is controlled at 6.0~8.0, cultivate taking-up in 12~24 hours, place 50 ℃~70 ℃ Water Tanks with Temp.-controlled, mix CaCl 2Solution produces rapidly precipitation, with its filtration, oven dry, is lime carbonate through X-ray diffraction analysis, and purity is very high, presents two kinds of crystal formations of vaterite and calcite (Fig. 3), granule-morphology as shown in Figure 4, multiple patterns such as spherical in shape, square, fusiform.
Embodiment 4
Bacterial strain Bacillus pasteurii is seeded to (medium component is as shown in table 1) in the triangular flask that substratum is housed, 25~37 ℃ of shaking culture in the constant-temperature shaking culture case, initial pH condition is controlled at 7.0, cultivates taking-up in 12~24 hours, mixes CaCl under the normal temperature 2Solution, and with MgSO 4Solution also mixes wherein as nucleator, adopt magnetic to stir 5~10min, produce precipitation rapidly, its filtration, oven dry, through X-ray diffraction analysis is calcite type calcium carbonate (Fig. 5), purity is very high, and granule-morphology as shown in Figure 6, and is spherical in shape, particle surface is fine and smooth, better dispersed, there is not agglomeration, grain diameter is decreased to about 0.3~1 μ m.

Claims (4)

1, a kind of method of utilizing microbe deposition to prepare lime carbonate, it is characterized in that bacterial strain Pasteur bacillus Bacillus pasteurii is seeded to and be equipped with on the substratum that contains the urea substrate, under 25~37 ℃, carry out shaking culture, and initial pH is controlled at 6.0~8.0, cultivated 12~24 hours, take out bacterium liquid, mix CaCl 2Solution, last, will produce precipitation and take out, filter, dry, can obtain lime carbonate.
2, the method for utilizing microbe deposition to prepare lime carbonate according to claim 1 is characterized in that taking-up bacterium liquid is heated to 50 ℃~70 ℃, and mix CaCl under 50 ℃~70 ℃ 2Solution.
3, the method for utilizing microbe deposition to prepare lime carbonate according to claim 1, it is characterized in that taking out bacterium liquid after, under room temperature, mix CaCl 2Solution.
4, the method for utilizing microbe deposition to prepare lime carbonate according to claim 3 is characterized in that mixing the MgSO as nucleator in the bacterium liquid that takes out 4Solution, and adopt magnetic to stir 5~10min.
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