CN110106164B - Photosynthetic bacterium immobilized substance and photosynthetic bacterium adsorbing material - Google Patents
Photosynthetic bacterium immobilized substance and photosynthetic bacterium adsorbing material Download PDFInfo
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Abstract
The invention provides a photosynthetic bacteria immobilized substance and a photosynthetic bacteria adsorbing material. The photosynthetic bacteria immobilized substance comprises photosynthetic bacteria, 2-3 parts of alginate gel and 3-5 parts of high-iron clay in parts by mass, the content of the photosynthetic bacteria in the photosynthetic bacteria immobilized substance is 0.06-240 hundred million/cubic centimeter, the photosynthetic bacteria immobilized substance takes a high-iron clay three-dimensional network structure as a framework, the framework is coated with the alginate gel and/or filled in the framework to form a plurality of micro spaces, and the photosynthetic bacteria is contained or enclosed in the micro spaces. The adsorbing material comprises a layered porous member and a photosynthetic bacteria immobilized substance, wherein the photosynthetic bacteria immobilized substance is arranged on or combined with the layered porous member. The photosynthetic bacteria immobilized substance has the advantages of reasonable design, convenient use, high immobilization density, good rigidity and high efficiency of treating heavy metals; the adsorbing material is convenient and efficient to use.
Description
Technical Field
The invention relates to the technical field of microorganisms, in particular to a photosynthetic bacteria immobilized substance and a photosynthetic bacteria adsorbing material, which are particularly suitable for recovering and treating high-valence metal chromium.
Background
Contamination with heavy metals is a serious problem. Once entering the environment, heavy metals are not decomposed in the environment like organic pollutants and can not be decayed for a long time. Although there is a chemical morphological transformation, many are irreversible processes and thus their presence cannot be eliminated from the environment, but rather remains in the environment for a long period of time. Heavy metals entering human bodies through various routes cannot be decomposed in vivo. Therefore, environmental pollution by heavy metals has attracted much attention. For example, the heavy metal element chromium is one of the main heavy metal pollution sources. The element chromium (Cr) has multiple valence states, such as divalent, trivalent, and hexavalent. The toxicity of chromium is strongly related to its valence state, where the Cr (VI) ion toxicity is the greatest, the Cr (II) and Cr (III) ions are the least, and the Cr (VI) toxicity is 100 times that of Cr (III). Thus, conversion of cr (vi) to cr (iii) is an effective detoxification means.
The traditional chromium removal method mainly adopts a chemical treatment method, generally comes from two ideas, namely a chemical method, an electrolytic method and the like, and has the defects of high energy and material consumption, poor removal effect of high-concentration wastewater, and generation of a large amount of toxic sludge in the removal process to cause secondary pollution. The second is an ion exchange method, an activated carbon method, or the like. The main disadvantage of such processes is the high cost of treating low concentration wastewater. Therefore, the methods of the two ideas are not suitable for large-area popularization.
Disclosure of Invention
In view of the deficiencies in the prior art, it is an object of the present invention to address one or more of the problems in the prior art as set forth above. For example, an object of the present invention is to provide a novel microorganism-adsorbing material.
In order to achieve the above object, an aspect of the present invention provides a photosynthetic bacteria immobilized substance. The photosynthetic bacteria immobilized substance comprises photosynthetic bacteria, 2-3 parts of alginate gel and 3-5 parts of high-iron clay in parts by mass, the content of the photosynthetic bacteria in the photosynthetic bacteria immobilized substance can be 0.06-240 hundred million/cubic centimeter, the photosynthetic bacteria immobilized substance takes a high-iron clay three-dimensional network structure as a framework, the framework is coated with the alginate gel and/or filled in the framework to form a plurality of micro spaces, and the photosynthetic bacteria is contained or enclosed in the plurality of micro spaces.
In an exemplary embodiment of the photosynthetic bacteria immobilized object of the present invention, the high iron clay may contain 2 to 15% by mass of trivalent iron oxide.
In an exemplary embodiment of the photosynthetic bacteria immobilized object of the present invention, the high-iron clay may be composed of high-iron attapulgite clay and high-iron diatomite, and a mass ratio of the high-iron attapulgite clay to the high-iron diatomite may be 1:1 to 10: 1.
In an exemplary embodiment of the photosynthetic bacteria immobilizate of the present invention, the micro-space size may be 0.1 μm to 200 μm.
In an exemplary embodiment of the photosynthetic bacteria immobilizer of the present invention, the photosynthetic bacteria immobilizer is spherical and may have a radial dimension of 0.1mm to 6 mm.
In an exemplary embodiment of the photosynthetic bacteria immobilizer of the present invention, the alginate gel may be one or a combination of calcium alginate gel and ferrous alginate gel. Further, the alginate gel can be obtained by the cross-linking reaction of sodium alginate and divalent metal ions.
In an exemplary embodiment of the photosynthetic bacteria immobilizate of the present invention, the photosynthetic bacteria may be rhodopseudomonas photosynthetic bacteria.
Another aspect of the present invention provides a photosynthetic bacteria adsorbent material, which may include a layered porous member and a photosynthetic bacteria immobilizer as described above, disposed on or attached to the layered porous member.
In an exemplary embodiment of the photosynthetic bacteria adsorbent material of the present invention, the photosynthetic bacteria adsorbent material may be a layered structure or a porous three-dimensional structure.
Compared with the prior art, the photosynthetic bacteria immobilized substance has the advantages of reasonable design, convenient use, high immobilization density, good rigidity and high efficiency of treating heavy metals; the adsorption material has reasonable structural design and rapid and efficient use.
Drawings
The above and other objects and features of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 shows a scanning electron microscope image of immobilized photosynthetic bacteria according to an exemplary embodiment of the present invention;
fig. 2 shows a scanning electron microscope image of high-iron clay according to an exemplary embodiment of the invention, wherein, the image a is a scanning electron microscope image of high-iron diatomite, and the image b is a scanning electron microscope image of high-iron attapulgite clay.
Detailed Description
Hereinafter, the photosynthetic bacteria immobilized matter and the photosynthetic bacteria adsorbing material according to the present invention will be described in detail with reference to the accompanying drawings and exemplary embodiments.
Specifically, the sodium alginate is an acidic anionic polysaccharide extracted from brown algae and thalli, and the gel formed by the sodium alginate and divalent metal cations is used as a carrier, so that the gel has the advantages of small toxicity to microorganisms, high immobilization density and good rigidity. The high-iron clay is also a good carrier in the immobilization of bacteria, and the porous, lamellar and rod-shaped three-dimensional network structure formed by the porous, lamellar and rod-shaped minerals can provide enough micro space in the gel microspheres for microorganisms. Compared with the traditional carrier material, the high-iron clay (high-iron attapulgite, high-iron diatomite) has the advantages of easily available raw materials, high mechanical strength, good mass transfer performance, high environmental adaptability, good permeability, large specific surface area, low cost and the like. Taking a proper amount of high-iron clay, and obtaining the usable high-iron clay raw material through the processes of grinding, sieving, washing, drying and the like. Compared with the traditional carrier material, the high-iron clay (high-iron attapulgite and high-iron diatomite) has reducibility due to the rich Fe (III) (ferric iron) which can be reduced by photosynthetic bacteria, and can act synergistically with the photosynthetic bacteria to improve the heavy metal removal efficiency.
The photosynthetic bacteria are mixed with sodium alginate and high-iron clay (high-iron attapulgite and high-iron diatomite) according to a certain proportion, and the photosynthetic bacteria are immobilized to prepare a photosynthetic bacteria immobilized substance (microcapsule) with certain rigidity. Due to the photosynthetic bacteria, the Fe (III) in the high-iron clay (high-iron attapulgite and high-iron diatomite) can be reduced into Fe (II) (ferrous iron) to ensure that the Fe (III) has certain reducibility. The photosynthetic bacteria and the high-iron clay (high-iron attapulgite and high-iron diatomite) synergistically act to reduce high-valence heavy metals such as Cr (VI) (hexavalent chromium ions), and the alginate and the high-iron clay (high-iron attapulgite and high-iron diatomite) are combined to adsorb the heavy metals, so that the heavy metal treatment efficiency is improved. In addition, the alginate and the high-iron clay (high-iron attapulgite and high-iron diatomite) form a composite three-dimensional network structure, so that enough space is provided for the photosynthetic bacteria, and the immobilization of the photosynthetic bacteria is facilitated.
FIG. 1 is a scanning electron microscope image of immobilized photosynthetic bacteria according to an exemplary embodiment of the present invention, wherein FIGS. a and b are scanning electron microscope images with different sizes; fig. 2 shows a scanning electron microscope image of high-iron clay according to an exemplary embodiment of the invention, wherein, the image a is a scanning electron microscope image of high-iron diatomite, and the image b is a scanning electron microscope image of high-iron attapulgite clay.
One aspect of the present invention provides a photosynthetic bacteria immobilized substance. In an exemplary embodiment of the photosynthetic bacteria immobilized object of the present invention, the photosynthetic bacteria immobilized object is composed of photosynthetic bacteria, 2 to 3 parts by mass of alginate gel and 3 to 5 parts by mass of high-iron clay, and the volume density of the photosynthetic bacteria in the photosynthetic bacteria immobilized object may be 0.06 to 240 hundred million/cubic centimeter (hundred million/cubic centimeter). Further, the photosynthetic bacteria immobilized material comprises 2.2-3 parts by mass of alginate gel and 3-4.7 parts by mass of high-iron clay, wherein the volume density of the photosynthetic bacteria immobilized material can be 0.10-200 hundred million/cubic centimeter, and further the volume density of the photosynthetic bacteria immobilized material can be 0.25-185 hundred million/cubic centimeter, for example, 150 hundred million/cubic centimeter. The inventor researches and discovers that: for the photosynthetic bacteria volume density, the volume density is too low, and the efficiency of reduction treatment of high-valence chromium by the photosynthetic bacteria immobilized compound is low; with the increase of the volume density of the photosynthetic bacteria, the efficiency of reducing high-valence chromium ions is not obviously improved, and the waste of the photosynthetic bacteria and the increase of the cost are caused by the overhigh volume density of the photosynthetic bacteria. Therefore, the volume density of the photosynthetic bacteria is set. The processing method utilizes the synergistic action of photosynthetic bacteria in the photosynthetic bacteria immobilized matter and the high-iron clay to convert hexavalent chromium ions in the chromium-containing solution into low-dissolved trivalent chromium ions or lower-valent chromium ions and solidify the low-dissolved trivalent chromium ions or lower-valent chromium ions.
The porous, lamellar and rodlike minerals formed by the high-iron clay used in the invention have communicated porous structures of micron and submicron level; the alginate gel has a good network structure, such as a good three-dimensional network structure, can provide enough space for the immobilization of photosynthetic bacteria, is favorable for the transfer of pollutants in the three-dimensional network structure, and improves the treatment efficiency. As shown in figure 1, the photosynthetic bacteria immobilized substance is a porous three-dimensional network structure formed by porous, lamellar and rod-shaped minerals of the high-iron clay as a framework, alginate gel can be filled in the framework and/or coats a part or all of the framework, micro-spaces and micro-capsules communicated with the micro-spaces can be formed between the alginate gel and the high diatomite, the photosynthetic bacteria are contained or enclosed in the formed micro-spaces or micro-capsules, and the photosynthetic bacteria can be well immobilized through the synergistic action of the sodium alginate and the high-iron clay. Due to the alginate gel and the high-iron clay porous network structure, the diffusion of pollutants in the network structure can be improved, and the treatment efficiency of treating heavy metals is further improved. For example, the interconnected micro-spaces in the photosynthetic bacteria immobilized material can further improve the removal of pollutants and the diffusion of photosynthetic bacteria in the photosynthetic bacteria immobilized material.
As described above, with respect to the ratio of the photosynthetic bacteria immobilized substance provided by the present invention, if the content of alginate is too low, the photosynthetic bacteria immobilized substance cannot be formed, for example, when the ratio of the photosynthetic bacteria immobilized substance reaches 2% sodium alginate to 7% high-iron diatomite, the immobilized substance cannot be formed into a sphere or other shapes due to too low content of sodium alginate; if the content of the high-iron clay is too high, the concentration of the mixed solution of alginate and the high-iron clay is too high, and the photosynthetic bacteria immobilized substance can hardly form a good spherical shape and only can form a strip-shaped or columnar fixed object. And is easily broken in the solution even when molded, affecting the removal of chromium ions. Further, the photosynthetic bacteria immobilized substance can comprise 2.2-2.8 parts of alginate gel and 3.3-4.7 parts of high-iron clay in parts by weight. Furthermore, the photosynthetic bacteria immobilized substance can contain 2.2-2.6 parts of alginate gel and 3.4-4.5 parts of high-iron clay in parts by weight. For example, the photosynthetic bacteria immobilized material may contain 2.6 parts by mass of alginate gel and 3.8 parts by mass of high-iron clay.
Further, the photosynthetic bacteria used in the present invention are derived from concentrated photosynthetic bacteria liquid. The volume of the concentrated photosynthetic bacteria liquid can be 2-10 mL, and the concentration of the photosynthetic bacteria in the concentrated photosynthetic bacteria liquid can be 30-100 hundred million/mL. Namely, the volume and the density of the concentrated photosynthetic bacteria liquid correspond to 2-3 parts of alginate gel and 3-5 parts of high-iron clay in parts by mass.
In this example, the ferric oxide (Fe) in the high-iron clay is calculated by mass percentage2O3) Can be 2-15%. The higher the content of ferric iron, the more ferrous it can be reduced to, theoretically, the more favourable the reduction of chromium is for the elemental iron content of the high iron clay, but in practice the applicant has found that with increasing ferric iron the handling properties show an increasing and then decreasing regime. Thus, the present invention controls ferric oxide (Fe) in the high iron clay2O3) 2 to 15 percent (mass). Further, the content of the trivalent iron oxide may be 4% to 13%. Furthermore, the content of the ferric oxide is 8 percent, and the treatment effect can be optimal.
In this example, the high-iron clay may be a mixture of high-iron attapulgite clay and high-iron diatomaceous earth. The mass ratio of the high-iron attapulgite clay to the high-iron diatomite can be 1: 1-10: 1. The high-iron diatomite provides a porous microstructure and improves permeability; the high-iron attapulgite clay is beneficial to the cementation property. The mass ratio of the above arrangement can ensure that the photosynthetic bacteria immobilized substance has enough porous microstructure and also can ensure that the photosynthetic bacteria immobilized substance has better permeability. Further, the mass ratio of the high-iron attapulgite clay to the high-iron diatomite can be 1: 1-8: 1. For example, it may be 1: 6. For example, as shown in fig. 2, both high-iron attapulgite clay and high-iron diatomaceous earth exhibit a porous, lamellar, and rod-like micro-mineral structure. The high-iron clay is a good carrier in the fixation of photosynthetic bacteria, has small granularity and is easy to form colloid. Compared with common inorganic mineral carrier materials, the material is easy to obtain, the mechanical strength is high, the mass transfer performance is good, the environmental adaptability is high, the permeability is good, the specific surface area is large, the cost is low, and the like.
In this embodiment, the photosynthetic bacteria immobilized object is a spherical photosynthetic bacteria immobilized object, and the radial dimension of the spherical photosynthetic bacteria immobilized object may be 0.1mm to 6 mm. Of course, the shape of the photosynthetic bacteria immobilized product of the present invention is not limited thereto, and the photosynthetic bacteria immobilized product may be prepared in the form of granules. When the photosynthetic bacteria immobilized substance is prepared in the form of granules, the particle size may be 1mm to 6mm, preferably, 2mm to 5 mm. Further, a filter layer or a porous material formed of particles may be used. Of course, the size of the photosynthetic bacteria immobilized substance of the present invention is not limited thereto, and the size may be adjusted accordingly according to the concentration of chromium to be treated.
In the present embodiment, the size of the micro-space is 0.1 μm to 200 μm. Further, the size of the micro-space is 20 μm to 180 μm. For example, the size of the micro-space may be 120 μm. The micro-space size refers to the distance from the center point of the micro-space to the boundary of the micro-space. The micro-space size can well fix the photosynthetic bacteria, ensure the density of the photosynthetic bacteria in unit area in the immobilized substance, and can efficiently treat heavy metals.
In this embodiment, the alginate gel may be one or a combination of calcium alginate gel and ferrous alginate gel. The alginate gel of the invention can be prepared by cross-linking reaction of sodium alginate and divalent metal cations. For example, the calcium alginate gel can be obtained by the cross-linking reaction of sodium alginate and calcium ions, and the ferrous alginate gel can be obtained by the cross-linking reaction of sodium alginate and ferrous ions. That is, the aqueous divalent metal salt solution may be an aqueous calcium ion salt solution or an aqueous ferrous ion salt solution.
In this embodiment, the photosynthetic bacteria refer to prokaryotes that can use a light source as an energy source, and are widely distributed in various water areas, soils, and sludges. For example, the photosynthetic bacteria can be rhodopseudomonas photosynthetic bacteria, e.g., rhodopseudomonas palustris photosynthetic bacteria.
In this embodiment, for example, the photosynthetic bacteria immobilized compound can be prepared by the following method: after co-culturing the high-iron clay and the photosynthetic bacteria, carrying out centrifugal treatment, and removing supernatant to obtain a first concentrated bacterium liquid mixture (the volume can be 2-10 mL, and the concentration of the photosynthetic bacteria can be 30-100 hundred million/mL); uniformly mixing a sodium alginate solution with the first mixture to obtain a second mixed solution; the second mixed solution is evenly injected into a divalent metal salt solution (such as CaCl with the mass concentration of 2-5 percent)2In solution), sodium alginate with divalent metal ions (e.g., Ca)2+) And (3) crosslinking to form gel, immobilizing the photosynthetic bacteria to form composite hydrogel microspheres, and stabilizing to obtain the photosynthetic bacteria immobilized substance. Of course, the method for producing the photosynthetic bacteria immobilized product of the present invention is not limited thereto, and other methods capable of forming the photosynthetic bacteria immobilized product of the present invention are also possible.
In another aspect of the invention, a photosynthetic bacteria adsorbent material is provided. In an exemplary embodiment of the photosynthetic bacteria adsorbent material of the present invention, the adsorbent material comprises a layered porous member and the photosynthetic bacteria immobilizer described above. The photosynthetic bacteria immobilizer is disposed on or bound to the layered porous structure.
In this example, the photosynthetic bacteria adsorbent material may be a layered structure or a porous three-dimensional structure. For example, the photosynthetic bacteria adsorbent may have a spherical three-dimensional porous structure, a bowl-shaped or cylindrical three-dimensional porous structure, or the like.
The layered porous member may be a plastic mesh, a metal mesh, a corrosion-resistant metal fiber mesh, or the like, but the layered porous member of the present invention is not limited thereto. The bonding or disposing manner here may be adhesion or adsorption on the porous member. For example, the photosynthetic bacteria immobilizate may be formed into particles and disposed between two layers of porous members, thereby forming an adsorbent material.
In conclusion, the photosynthetic bacteria immobilized substance is convenient to use and reasonable in design, can efficiently treat heavy metal ions in solution (wastewater), and does not produce secondary pollution. The adsorbing material is used quickly and efficiently.
Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A photosynthetic bacteria immobilized substance is characterized by comprising photosynthetic bacteria, 2-3 parts by mass of alginate gel and 3-5 parts by mass of high-iron clay, wherein the content of the photosynthetic bacteria in the photosynthetic bacteria immobilized substance is 0.06-240 hundred million/cubic centimeter, the photosynthetic bacteria immobilized substance takes a high-iron clay three-dimensional network structure as a framework, the framework is coated with the alginate gel and/or filled in the framework to form a plurality of micro spaces, the photosynthetic bacteria are contained or enclosed in the plurality of micro spaces, the alginate gel is obtained after cross-linking reaction of sodium alginate and divalent metal ions, the size of the micro spaces is 0.1-200 mu m, and the high-iron clay contains 2-15% by mass of trivalent iron oxide, the photosynthetic bacteria immobilized compound reduces high-valence heavy metals through the synergistic action of the photosynthetic bacteria and the high-iron clay, and simultaneously combines the adsorption capacity of alginate and the high-iron clay to the heavy metals.
2. A photosynthetic bacteria immobilized substance according to claim 1, wherein the high-iron clay comprises high-iron attapulgite clay and high-iron diatomite in a mass ratio of 1: 1-10: 1.
3. A photosynthetic bacteria immobilized substance according to claim 1 wherein the photosynthetic bacteria immobilized substance is spherical and has a radial dimension of 0.1mm to 6 mm.
4. A photosynthetic bacteria immobilized substance according to claim 1 wherein the alginate gel is one or a combination of calcium alginate gel and ferrous alginate gel.
5. A photosynthetic bacteria immobilized species according to claim 1 wherein the photosynthetic bacteria is a photosynthetic bacteria of the genus rhodopseudomonas.
6. A photosynthetic bacteria adsorbent comprising a layered porous member and the photosynthetic bacteria immobilized substance according to claim 1, wherein the photosynthetic bacteria immobilized substance is provided on or bonded to the layered porous member.
7. A photosynthetic bacteria adsorbing material according to claim 6, wherein the photosynthetic bacteria adsorbing material is a layered structure or a porous three-dimensional structure.
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