CN110106164A - Photosynthetic bacteria fixed compound and photosynthetic bacteria adsorbent material - Google Patents
Photosynthetic bacteria fixed compound and photosynthetic bacteria adsorbent material Download PDFInfo
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- CN110106164A CN110106164A CN201910411357.1A CN201910411357A CN110106164A CN 110106164 A CN110106164 A CN 110106164A CN 201910411357 A CN201910411357 A CN 201910411357A CN 110106164 A CN110106164 A CN 110106164A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
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Abstract
The present invention provides a kind of photosynthetic bacteria fixed compound and photosynthetic bacteria adsorbent materials.The photosynthetic bacteria fixed compound includes forming by photosynthetic bacteria and according to 2~3 parts of alginates of mass fraction meter and 3~5 parts of high clunches, photosynthetic bacteria content in the photosynthetic bacteria fixed compound is 0.06 hundred million/cubic centimetre~24,000,000,000/cubic centimetre, and the photosynthetic bacteria fixed compound is using high clunch three-dimensional net structure as skeleton, it coats the skeleton with alginate and/or is filled in the skeleton, to form multiple micro- spaces, photosynthetic bacteria is received or is enclosed in the multiple micro- space.Adsorbent material includes layered porous component and photosynthetic bacteria fixed compound, and photosynthetic bacteria fixed compound is arranged or is incorporated on layered porous member.Rationally, easy to use, immobilization density is high, and rigidity is good, and processing heavy metal is high-efficient for photosynthetic bacteria fixed compound design of the invention；Adsorbent material is easy to use efficiently.
Description
Technical field
The present invention relates to microorganisms technical fields, more particularly, are related to a kind of photosynthetic bacteria fixed compound and photosynthetic thin
Bacterium adsorbent material is particularly suitable for the recovery processing to high-valency metal chromium.
Background technique
The pollution of heavy metal is a very serious problem.Heavy metal after entering environment, unlike organic pollutant that
Sample can decompose in the environment, and be possible to lasting.It is much irreversible although this has the transformation in terms of chemical form
Process, thus its presence cannot be eliminated from environment, and can remain in environment for a long time.Enter a huge sum of money for human body by various approach
Belong to, will not decompose in vivo.Therefore, the environmental pollution of heavy metal has caused the very big concern of people.For example, heavy metal element
Chromium is exactly one of main source of heavy metal pollution.Elemental chromium (Cr) has a variety of valence states such as divalent, trivalent and sexavalence.The toxicity of chromium
There are much relations with its valence state, wherein Cr (VI) ion toxicity is maximum, and Cr (II) and Cr (III) ion toxicity are minimum, Cr (VI)
Toxicity be 100 times of Cr (III).Therefore, converting Cr (III) for Cr (VI) is a kind of effective removing toxic substances mode.
Traditional chromium minimizing technology is mainly method of chemical treatment, generally speaking derives from two kinds of thinkings, the first is chemistry
Method, electrolysis method etc., such method have a defect that energy is larger with material consumption, and the removal effect of high-concentration waste water is poor,
And a large amount of toxic sludge can be generated in removal process, causes secondary pollution.Second is ion-exchange, activated carbon method
Deng.The major defect of such method is expensive when handling low concentration wastewater.Therefore, the method for both the above thinking is not
It is suitble to the popularization of large area.
Summary of the invention
It is above-mentioned existing in the prior art it is an object of the present invention to solving for the deficiencies in the prior art
One or more problems.For example, the purpose of the present invention is to provide a kind of novel microorganism adsorption materials.
To achieve the goals above, an aspect of of the present present invention provides a kind of photosynthetic bacteria fixed compound.It is described photosynthetic thin
Bacteria immobilization object includes by photosynthetic bacteria and according to 2~3 parts of alginates of mass fraction meter and 3~5 parts of high clunches
Composition, photosynthetic bacteria content in the photosynthetic bacteria fixed compound can for 0.06 hundred million/cubic centimetre~24,000,000,000/cube li
Rice, and the photosynthetic bacteria fixed compound is using high clunch three-dimensional net structure as skeleton is coated with alginate
It the skeleton and/or is filled in the skeleton, to form multiple micro- spaces, the photosynthetic bacteria is received or is enclosed in described
In multiple micro- spaces.
In an exemplary embodiment of the photosynthetic bacteria fixed compound of the invention, the high clunch can contain
There is based on quality percentage 2%~15% ferric oxide.
In an exemplary embodiment of the photosynthetic bacteria fixed compound of the invention, the high clunch can be by
High-speed rail Concave-convex clay rod and high-speed rail diatomite composition, the mass ratio of the high-speed rail Concave-convex clay rod and high-speed rail diatomite can be with
For 1:1~10:1.
In an exemplary embodiment of the photosynthetic bacteria fixed compound of the invention, micro- bulk can be with
It is 0.1 μm to 200 μm.
In an exemplary embodiment of the photosynthetic bacteria fixed compound of the invention, the photosynthetic bacteria immobilization
Object be it is spherical, radial dimension can be 0.1mm~6mm.
In an exemplary embodiment of the photosynthetic bacteria fixed compound of the invention, the alginate can
Think one of calcium alginate gel and alginic acid ferrous iron gel or combination.Further, the alginate can be with
By being obtained after sodium alginate and bivalent metal ion cross-linking reaction.
In an exemplary embodiment of the photosynthetic bacteria fixed compound of the invention, the photosynthetic bacteria can be
Rhodopseudomonas photosynthetic bacteria.
Another aspect provides a kind of photosynthetic bacteria adsorbent materials, and it is more that the adsorbent material may include stratiform
Pole and photosynthetic bacteria fixed compound as described above, the photosynthetic bacteria fixed compound are arranged or are incorporated in layered
On porous member.
In an exemplary embodiment of photosynthetic bacteria adsorbent material of the invention, the photosynthetic bacteria adsorbent material can
Think layer structure or porous three-dimensional structure.
Compared with prior art, photosynthetic bacteria fixed compound of the invention design is reasonable, easy to use, immobilization density
Height, rigidity is good, and processing heavy metal is high-efficient；Adsorbent material is reasonable in design, using quickly and efficiently.
Detailed description of the invention
By the description carried out with reference to the accompanying drawing, above and other purpose of the invention and feature will become more clear
Chu, in which:
Fig. 1 shows the photosynthetic bacteria fixed compound surface sweeping electron microscope of an illustrative embodiment of the invention；
Fig. 2 shows the high clunch scanning electron microscope (SEM) photographs of an illustrative embodiment of the invention, wherein figure a is high-speed rail silicon
Diatomaceous earth scanning electron microscope (SEM) photograph, figure b are high-speed rail Concave-convex clay rod scanning electron microscope (SEM) photograph.
Specific embodiment
Hereinafter, photosynthetic bacteria immobilization according to the present invention will be described in detail in conjunction with attached drawing and exemplary embodiment
Object and photosynthetic bacteria adsorbent material.
Specifically, sodium alginate is a kind of acidic anionic polysaccharide extracted from brown alga and thallus, and the present invention is with sea
The gel that mosanom and divalent metal are formed is carrier, has small to Ecotoxicology, immobilization density is high, rigidity compared with
Good advantage.High clunch is equally a kind of good carrier, porous, lamella, rodlike mineral formation in the fixation of bacterium
Poroid three-dimensional net structure enough micro- spaces can be provided in gel micro-ball to microorganism.(high-speed rail is concave-convex for high clunch
Stick stone, high-speed rail diatomite) compared with conventional carriers material, raw material is easy to get, high mechanical strength, mass-transfer performance are good, environmental suitability is high,
Permeability is good, large specific surface area, it is low in cost the advantages that.Take high clunch appropriate, by being ground up, sieved, washing, dry and waited
Available high-speed rail raw clay is obtained after journey.High clunch (high-speed rail attapulgite, high-speed rail diatomite) compared with conventional carriers material,
Due to making it have reproducibility, work can be cooperateed with photosynthetic bacteria rich in the Fe (III) (ferric iron) that can be restored by photosynthetic bacteria
With raising removal efficiency of heavy metals.
The present invention by by photosynthetic bacteria and sodium alginate and high clunch (high-speed rail attapulgite, high-speed rail diatomite) according to
Certain proportion mixing, by photosynthetic bacteria immobilization, is prepared into the photosynthetic bacteria fixed compound (micro-capsule) with certain rigidity.Due to
Photosynthetic bacteria has certain reproducibility, can be by the Fe (III) in high clunch (high-speed rail attapulgite, high-speed rail diatomite) also
Originally it is Fe (II) (ferrous iron), makes it have reproducibility.Pass through photosynthetic bacteria and high clunch (high-speed rail attapulgite, high-speed rail silicon
Diatomaceous earth) synergistic effect reduction high price heavy metal, for example, Cr (VI) (hexavalent chromium), viscous in combination with alginate and high-speed rail
Native (high-speed rail attapulgite, high-speed rail diatomite) improves heavy metal treatment effeciency to the adsorption capacity of heavy metal.In addition, of the invention
Alginate and high clunch (high-speed rail attapulgite, high-speed rail diatomite) are formed into compound three-dimensional net structure, provide foot
Enough spaces are conducive to the immobilization of photosynthetic bacteria to photosynthetic bacteria.
Fig. 1 shows the photosynthetic bacteria fixed compound surface sweeping electron microscope of an illustrative embodiment of the invention, wherein figure a
It is the scanning electron microscope (SEM) photograph of different up-sizings from figure b；Fig. 2 shows the scannings of the high clunch of an illustrative embodiment of the invention
Electron microscope, wherein figure a is high-speed rail diatomite scanning electron microscope (SEM) photograph, and figure b is high-speed rail Concave-convex clay rod scanning electron microscope (SEM) photograph.
An aspect of of the present present invention provides a kind of photosynthetic bacteria fixed compound.In photosynthetic bacteria fixed compound of the invention
In one exemplary embodiment, the photosynthetic bacteria fixed compound is by photosynthetic bacteria and according to 2~3 portions of seaweed of mass fraction meter
Hydrochlorate gel and 3~5 parts high clunch composition, the bulk density that the photosynthetic bacteria accounts for photosynthetic bacteria fixed compound can be
0.06 hundred million/cubic centimetre~24,000,000,000/cubic centimetre (hundred million/cubic centimetre).Further, according to mass fraction meter 2.2~3
Part alginate and 3~4.7 parts high clunch composition, the photosynthetic bacteria account for the bulk density of photosynthetic bacteria fixed compound
It can be 0.10 hundred million/cubic centimetre~20,000,000,000/cubic centimetre, further, the photosynthetic bacteria accounts for photosynthetic bacteria immobilization
The bulk density of object can be 0.25 hundred million/cubic centimetre~18,500,000,000/cubic centimetre, for example, can be 15,000,000,000/cubic centimetre.
Inventor studies discovery: for above-mentioned photosynthetic bacteria bulk density, bulk density is too low, the reduction of photosynthetic bacteria fixed compound
Handle the low efficiency of high valence chrome；With the increase of photosynthetic bacteria bulk density, the efficiency for restoring high price chromium ion is not obtained
It is obviously improved, the excessively high waste for being bound to cause photosynthetic bacteria of the volume density of photosynthetic bacteria, increases cost.Therefore, it is arranged above-mentioned
The bulk density of photosynthetic bacteria.The processing method is cooperateed with using the photosynthetic bacteria in photosynthetic bacteria fixed compound with high-speed rail clay
Effect converts the hexavalent chromium in chromium-containing solution to the trivalent chromic ion or more low price chromium ion and solid of low solubilised state
Change.
Porous, lamella that high clunch that the present invention uses is formed, rodlike mineral have micro- sodium rice, submicron order connection more
Pore structure；Alginate body has good network structure, such as can be photosynthetic with good three-dimensional net structure
Bacteria adhensionization provides enough spaces, and is conducive to transmitting of the pollutant in three-dimensional net structure, improves treatment effeciency.
As shown in Figure 1, photosynthetic bacteria fixed compound be exactly with the porous of high clunch, lamella, rodlike mineral formation poroid three dimensional network
Network structure is as skeleton, and alginate can be filled in skeleton and/or coat some or all of skeleton, in sea
The micro-capsule that just will form micro- space between alginate jelly and high diatomite and be connected to micro- space, photosynthetic bacteria be received or
It is enclosed in the micro- space to be formed or micro-capsule, fixed light can be very good by the synergistic effect of sodium alginate and high clunch
Close bacterium.Due to alginate and high clunch porous network structure, expansion of the pollutant in network structure can be improved
It dissipates, further increases the treatment effeciency of processing heavy metal.For example, the micro- space of the connection having in photosynthetic bacteria fixed compound,
It can be further improved the diffusion for needing to remove pollutant and photosynthetic bacteria inside photosynthetic bacteria fixed compound.
More than, for the ratio that the photosynthetic bacteria fixed compound that the present invention is arranged is constituted, if alginate contains
Measure too low, photosynthetic bacteria fixed compound cannot form, for example, when photosynthetic bacteria fixed compound proportion reach 2% sodium alginate with
When 7% high-speed rail diatomite, since sodium alginate content is too low, fixed compound cannot form spherical or other shapes；If high
The too high levels of clunch, the concentration that will cause alginate and the mixed liquor of high clunch is excessive, photosynthetic bacteria fixed compound
Can hardly be formed well it is spherical, be only capable of forming strip or column fixture.And it is easy to break in the solution molding
It splits, the removing of chromium ion is impacted.Further, the photosynthetic bacteria fixed compound can contain according to the mass fraction
2.2~2.8 parts of alginates, 3.3~4.7 parts of high clunches.Further, the photosynthetic bacteria fixed compound can be with
Contain 2.2~2.6 parts of alginates, 3.4~4.5 parts of high clunches according to the mass fraction.For example, the photosynthetic bacteria is solid
2.6 parts of alginates, 3.8 parts of high clunches can be contained according to the mass fraction by determining compound.
Further, solution of photosynthetic bacteria of the photosynthetic bacteria used in the present invention from concentration.The concentration it is photosynthetic
The volume of bacterium liquid can be 2mL~10mL, and the photosynthetic bacteria concentration in concentrating photosynthetic bacteria liquid can be 3,000,000,000/mL~100
Hundred million/mL.Corresponding 2~3 parts of alginates and 3 according to the mass fraction of the volume and density of i.e. above-mentioned concentrating photosynthetic bacteria liquid
~5 parts high clunch part.
In the present embodiment, by mass percentage, the ferric oxide (Fe in the high clunch2O3) can be
2%~15%.For the iron content in high clunch, ferric content is higher, the divalent that can be reduced into
Iron is also more, theoretically more advantageous to the reduction of chromium, but in the actual operation process, it has been found that with ferric increasing
More, process performance shows the state for first increasing and reducing afterwards.Therefore, the present invention controls the ferric oxide in high clunch
(Fe2O3) it is 2%~15% (quality).Further, the content of ferric oxide can be 4%~13%.More further,
The content of ferric oxide is 8%, and treatment effect can achieve most preferably at this time.
In the present embodiment, the high clunch can be the mixing of high-speed rail Concave-convex clay rod and high-speed rail diatomite composition
Object.The mass ratio of the high-speed rail Concave-convex clay rod and high-speed rail diatomite can be 1:1~10:1.High-speed rail diatomite provides porous
Micro-structure improves permeability；High-speed rail attapulgite clay is conducive to cementing properties.The mass ratio of above-mentioned setting both can ensure that photosynthetic bacteria
Fixed compound is also ensured that by enough porous microstructures with preferable permeability.Further, high-speed rail Concave-convex clay rod
Mass ratio with high-speed rail diatomite can be 1:1~8:1.For example, can be 1:6.For example, as shown in Fig. 2, high-speed rail attapulgite
Porous, lamella and rodlike micro- mineral structure is presented in clay and high-speed rail diatomite.High clunch is consolidated photosynthetic bacteria
It is a kind of good carrier in fixed, granularity is small, easy at colloid.Compared with common inorganic mineral carrier material, raw material is easy to get, is mechanical
Intensity is high, mass-transfer performance is good, environmental suitability is high, permeability is good, large specific surface area, it is low in cost the advantages that, porous, piece
The poroid three-dimensional net structure of layer, rodlike mineral formation, provides matrix for photosynthetic bacteria immobilization, can be good at as photosynthetic
The skeleton of bacteria adhension compound can form three-dimensional network structure with alginate, provide enough spaces to light
Bacterium is closed, the immobilization of photosynthetic bacteria is conducive to.
In the present embodiment, the photosynthetic bacteria fixed compound is spherical photosynthetic bacteria fixed compound, spherical photosynthetic bacteria
The radial dimension of fixed compound can be 0.1mm~6mm.Certainly, the shape of photosynthetic bacteria fixed compound of the invention is not limited to
This, photosynthetic bacteria fixed compound can be prepared into graininess.When photosynthetic bacteria fixed compound is prepared as graininess, partial size can be with
For 1mm~6mm, it is preferred that 2mm~5mm.In addition it is also possible to for the filter layer or porous material that are formed by particle.Certainly, originally
The size of the photosynthetic bacteria fixed compound of invention is without being limited thereto, and size can be adjusted correspondingly according to the concentration of processing chromium.
In the present embodiment, the size in micro- space is 0.1 μm to 200 μm.Further, the size in micro- space
It is 20 μm to 180 μm.For example, the size in micro- space can be 120 μm.Above-mentioned micro- bulk refers to micro- space center's point to micro-
The distance of space boundary.Above-mentioned micro- bulk, which is arranged, can be well fixed photosynthetic bacteria, it is ensured that photosynthetic bacteria is in fixation
The density of unit area in compound, can efficiently handle heavy metal.
In the present embodiment, the alginate can be one in calcium alginate gel and alginic acid ferrous iron gel
Kind or combination.Alginate of the invention can be to be prepared by sodium alginate and divalent metal cross-linking reaction
Alginate.For example, the calcium alginate gel can be reacted to obtain by sodium alginate with calcium ion crosslinking, the sea
Alginic acid ferrous iron gel can be by obtaining after sodium alginate and ferrous ion cross-linking reaction.The i.e. described divalent metal saline solution can be with
For calcium ion salts aqueous solution or ferrous ion saline solution.
In the present embodiment, the photosynthetic bacteria refers to the prokaryotes that can use light source as energy source, extensively
It is distributed in all kinds of waters, soil, photosynthetic bacteria in sludge.For example, the photosynthetic bacteria can be photosynthetic thin for Rhodopseudomonas
Bacterium, for example, Rhodopseudomonas palustris category photosynthetic bacteria.
In the present embodiment, for example, the photosynthetic bacteria fixed compound can be prepared by following methods: high-speed rail is glued
After soil is co-cultured with photosynthetic bacteria, centrifugal treating removes supernatant, and obtaining concentration the first mixture of bacterium solution, (volume can be 2mL
~10mL, photosynthetic bacteria concentration can be 3,000,000,000/mL~10,000,000,000/mL)；Sodium alginate soln and first mixture is equal
Even mixing obtains the second mixed liquor；Second mixed liquor is injected uniformly in divalent metal salting liquid (such as mass concentration 2%
~5%CaCl2Solution) in, sodium alginate and bivalent metal ion (such as Ca2+) be cross-linked to form gel and fix photosynthetic bacteria
After change, composite hydrogel microballoon is formed, after stablizing, photosynthetic bacteria fixed compound can be obtained.Certainly, photosynthetic bacteria of the invention
The preparation method of fixed compound is without being limited thereto, other are capable of forming the method for photosynthetic bacteria fixed compound of the invention.
Another aspect provides a kind of photosynthetic bacteria adsorbent materials.In photosynthetic bacteria adsorbent material of the invention
An exemplary embodiment in, the adsorbent material include layered porous component and above-described photosynthetic bacteria immobilization
Object.Photosynthetic bacteria fixed compound is arranged or is incorporated on layered porous member.
In this example, photosynthetic bacteria adsorbent material can be layer structure or porous three-dimensional structure.For example, photosynthetic
Bacterial adsorption material can be spherical three-dimensional porous structure, be also possible to bowl-shape, columned three-dimensional porous structure etc..
More than, layered porous component here can be plastic silk screen, metal mesh, corrosion resistant metal web etc., certainly
Layered porous component of the invention is without being limited thereto.Here combination or set-up mode can be adherency or be adsorbed on porous structure
On part.For example, photosynthetic bacteria fixed compound can form particle, and it is arranged between two layers of porous member, to form absorption
Material.
In conclusion photosynthetic bacteria fixed compound of the invention is easy to use, design rationally, being capable of efficiently processing solution
Heavy metal ion in (waste water), and secondary pollution will not be generated.Adsorbent material is using quickly and efficiently.
Although those skilled in the art should be clear above by combining exemplary embodiment to describe the present invention
Chu can carry out exemplary embodiment of the present invention each without departing from the spirit and scope defined by the claims
Kind modifications and changes.
Claims (10)
1. a kind of photosynthetic bacteria fixed compound, which is characterized in that the photosynthetic bacteria fixed compound include photosynthetic bacteria and by
It is photosynthetic thin in the photosynthetic bacteria fixed compound according to 2~3 parts of alginates of mass fraction meter and 3~5 parts of high clunches
Bacterial content is 0.06 hundred million/cubic centimetre~24,000,000,000/cubic centimetre, and the photosynthetic bacteria fixed compound is with high clunch three
Dimension network structure is skeleton, is coated the skeleton with alginate and/or is filled in the skeleton, multiple to be formed
Micro- space, the photosynthetic bacteria are received or are enclosed in the multiple micro- space.
2. photosynthetic bacteria fixed compound according to claim 1, which is characterized in that the high clunch contains by quality hundred
Divide the ferric oxide of meter 2%~15%.
3. photosynthetic bacteria fixed compound according to claim 1 or 2, which is characterized in that the high clunch is recessed by high-speed rail
The mass ratio of convex stick stone clay and high-speed rail diatomite composition, the high-speed rail Concave-convex clay rod and high-speed rail diatomite is 1:1~10:
1。
4. photosynthetic bacteria fixed compound according to claim 1 or 2, which is characterized in that micro- bulk is 0.1 μm
To 200 μm.
5. photosynthetic bacteria fixed compound according to claim 1 or 2, which is characterized in that the photosynthetic bacteria fixed compound
To be spherical, radial dimension is 0.1mm~6mm.
6. photosynthetic bacteria fixed compound according to claim 1 or 2, which is characterized in that the alginate is by sea
It is obtained after mosanom and bivalent metal ion cross-linking reaction.
7. photosynthetic bacteria fixed compound according to claim 6, which is characterized in that the alginate is alginic acid
One of calcium gel and alginic acid ferrous iron gel or combination.
8. photosynthetic bacteria fixed compound according to claim 1 or 2, which is characterized in that the photosynthetic bacteria is red false single
Born of the same parents Pseudomonas photosynthetic bacteria.
9. a kind of photosynthetic bacteria adsorbent material, which is characterized in that the adsorbent material includes layered porous component and such as right
It is required that photosynthetic bacteria fixed compound described in 1, the photosynthetic bacteria fixed compound is arranged or is incorporated in layered porous member
On.
10. photosynthetic bacteria adsorbent material according to claim 9, which is characterized in that the photosynthetic bacteria adsorbent material is
Layer structure or porous three-dimensional structure.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111137985A (en) * | 2020-01-08 | 2020-05-12 | 西南科技大学 | Preparation method of microbial degradation material for treating ammonia nitrogen in sewage |
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