CN105483110A - Fe3O4 Magnetic nanoparticle immobilized Thialkalivibrio versutus and desulfurization process thereof - Google Patents
Fe3O4 Magnetic nanoparticle immobilized Thialkalivibrio versutus and desulfurization process thereof Download PDFInfo
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Abstract
The invention discloses immobilized Thialkalivibrio versutus based on Fe3O4 magnetic nanoparticles, a preparation method thereof and a desulfurization process using the immobilized Thialkalivibrio versutus. The immobilized Thialkalivibrio versutus has higher desulfurization efficiency and reusable, effectively overcoming the defects that Thioalkalivibrio versutus D301 has a long growth cycle and low cell quantity; in addition, compared with free Thioalkalivibrio, the immobilized Thialkalivibrio versutus reduces absorption of elemental sulfur, thus reducing further oxidization of the elemental sulfur and facilitating the separation and purification of the elemental sulfur.
Description
Technical field
The present invention relates to immobilized microorganism technology field, particularly relate to a kind of based on Fe
3o
4the immobilization sulphur alkali vibrios of magnetic nanoparticle, its preparation method and use its sulfur removal technology.
Background technology
Sulphur cycle, as integral part main in geochemical cycle, plays an important role in human being's production life.Particularly in recent years, along with environment ground constantly worsens, take acid rain as the sulphur pollution of representative, bring great threat to the existence of the mankind.The sulfurous gas that acid rain is mainly produced by combustion of fossil fuel and volcanic eruption produces through oxidation.Sweet natural gas, as the one of fossil oil, can produce sulfurous gas in combustion.Mainly because containing a certain amount of hydrogen sulfide in Sweet natural gas, not only there is strong corrosive nature to equipment such as drilling well, sleeve pipe, gathering lines, and the sulfur dioxide pollution environment produced.The sulfide contained in Sweet natural gas has H
2s, mercaptan, thioether, dithiocarbonic anhydride and carbonyl sulfide, the main object of wherein Sweet natural gas biological desulfurization process process is H
2s, hydrogen sulfide (H
2s) be a kind of hypertoxic gas, to all toxic effect of animal, microorganism, also can cause the poisoning of catalyst of petroleum refining process, reduce product yield, cause equipment and corrosion of piping, reduce work-ing life.Therefore, desulfurization is the important procedure of oil and natural gas oil-gas gathering and transportation process and petroleum chemicals processing.
At present, the method for hydrogen sulfide stripping mainly contains physisorphtion, chemical method, membrane separation process and biological process.Physical adsorption mainly adopts organic solvent and porous adsorbing material, but organic solvent absorption needs to operate under the environment of low temperature, high pressure, requires higher to the material of equipment.And porous adsorbing material is as gac, adsorption rate is low, and along with the increase of saturation ratio, efficiency reduces.Although there is report gac to may be used for the deep desulfuration of hydrogen sulfide, biogas is after thermal treatment active carbon desulfurization, and hydrogen sulfide content can drop to below 0.5ppm.But, it is very complicated that gac removes hydrogen sulfide reaction, the impact of the series of physical of sorbent suspension and gas and chemical property (see, MonteleoneG, deFrancescoM, GalliS, MarchettiM, NaticchioniV.ChemicalEngineeringJournal, 2011,173 (2): 407-414).Chemical method removes hydrogen sulfide and is divided into chemiadsorption and chemical oxidization method, the former utilizes basic solution that hydrogen sulfide reaction is generated corresponding salt, the latter utilizes chemical oxidizing agent by Oxidation of Hydrogen Sulfide in oil and natural gas, biological desulfurizing technology has the advantage such as economy, environmental protection, and correlative study at home and abroad in recent years all shows with application the impetus increased fast.H
2the removing sulfuldioxide of S mainly contains LO-CAT technique, Amine-Claus technique, membrane separation process and biological desulphurization etc.Microbial desulfurization utilizes the metabolism of microorganism by H
2s is converted into elemental sulfur etc.Be that the amine of basic solution absorbs with alkanolamine be the main method of natural gas conditioning, as thanomin, diethanolamine, diglycolamine, diisopropanolamine (DIPA), N methyldiethanol amine etc., the method needs at high temperature usually, and expensive raw material price.Iron oxide process is a kind of conventional sulfur method in chemical oxidization method, is mainly used in thick desulfurization and lean sulphurous gas essence is de-.Biological desulphurization has less energy-consumption, high-level efficiency, equipment simply, not produce the advantages such as secondary pollution.But the microorganism adopted in traditional biological desulphurization is responsive to environmental change, process control is complicated.
Be the strain obligate autotrophy type sulfur-oxidizing bacteria that this laboratory is separated to from Ordos, inner Mongolia salt alkali lake addicted to salt basophilic sulphur alkali vibrios ThioalkalivibrioversutusD301 (CGMCCNo.8497), it utilizes HCO
3 -as carbon source, the inorganic sulfur mixture of reductibility, as sulphur source, is under the jurisdiction of sulphur alkali Vibrio.The feature of this microorganism belonging to genus be obligate addicted to salt basophilic, can sulfide oxidation, thiosulphate, elemental sulfur, sulphite, polythionate (see, SorokinDY, KuenenJG, JettenM, ArchMicrobiol, 2001; 175:94-101; SorokinDY, AntipovAN, KuenenJG, ArchMicrobiol2003; 180:127-133.).The growth pH scope of this genus bacterium is between 7.5 ~ 10.65, between Na ion concentration 0.2 ~ 4M.ThioalkalivibrioversutusD301, except playing except keying action in the sulphur cycle of salt alkali lake, also has a good application prospect in waste water and waste gas biological removal of sulphide.
Although ThioalkalivibrioversutusD301 has lot of advantages, but still there is many problems in actual applications.First, it is a kind of autotrophic microorganism, and growth cycle is long, and cell concentration is few; Secondly, grow into the later stage, cell is easy to be combined with the sulphur homojunction produced, and is unfavorable for the separation of sulphur simple substance; Further, sulphur simple substance and Cell binding, accelerate the further oxidation of sulphur simple substance, be unfavorable for the accumulation of sulphur simple substance.For above-mentioned defect, cell fixation can be adopted to solve: on the one hand, be realized the repeatedly recycling of cell by cell fixation, slow to solve Growth of Cells, the problem that biomass is low; On the other hand, reduced the combination of cell and sulphur simple substance by cell fixation, thus the accumulation being beneficial to later stage elemental sulfur be separated.
At present, the method for conventional cell fixation has entrapping method and absorption method.Entrapping method, has good biocompatibility, and immobilization efficiency is high, low cost and other advantages, and range of application is wider; But traditional entrapping method resistance to mass transfer and greatly sterically hindered, thus biological activity is lower.Absorption method, reduces traditional entrapping method resistance to mass transfer, but, be limited to biomass charge capacity, bonding force, biology catalytic activity, and operational stability.
Summary of the invention
For the above-mentioned problem existing in actual applications addicted to salt basophilic sulphur alkali vibrios ThioalkalivibrioversutusD301 (CGMCCNo.8497), the present invention proposes a kind of based on Fe
3o
4the immobilization sulphur alkali vibrios of magnetic nanoparticle, its preparation method and use its sulfur removal technology.Fe of the present invention
3o
4the desulphurizing activated height of magnetic nano particle immobilized sulphur alkali vibrios, reusable; And decrease the absorption with elemental sulfur, thus reduce the further oxidation of elemental sulfur, be convenient to the separation and purification of elemental sulfur.
For reaching this object, the present invention by the following technical solutions:
First aspect, the invention provides a kind of based on Fe
3o
4the immobilization sulphur alkali vibrios of magnetic nanoparticle, it is by making Fe
3o
4magnetic nanoparticle is adsorbed on addicted to the cell surface of salt basophilic sulphur alkali vibrios ThioalkalivibrioversutusD301 (CGMCCNo.8497) and obtains;
As preferably, described Fe
3o
4magnetic nanoparticle is Fe
3o
4superparamagnetic nano particle;
Preferably, described Fe
3o
4the diameter of magnetic nanoparticle is 10-50nm, is preferably 10 ~ 20nm;
Preferably, described Fe
3o
4magnetic nanoparticle adopts coprecipitation method to obtain.
Describedly be preserved in China Committee for Culture Collection of Microorganisms's common micro-organisms center (CGMCC) addicted to salt basophilic sulphur alkali vibrios ThioalkalivibrioversutusD301, its address is: No. 3, Yard 1, BeiChen xi Road, Chaoyang District, Beijing City, Institute of Microorganism, Academia Sinica, postcode: 100101; Preservation date is on November 25th, 2013, and deposit number is CGMCCNo.8497.
The present invention is based on Fe
3o
4the immobilization sulphur alkali vibrios of magnetic nanoparticle has higher desulfuration efficiency, up to more than 95%, suitable with the desulfuration efficiency of free sulphur alkali vibrios; Under the effect of externally-applied magnetic field, be easy to realize reclaiming, regenerating, and after recycling 3-6 time, still keep higher desulfuration efficiency, effectively overcome addicted to salt basophilic sulphur alkali vibrios ThioalkalivibrioversutusD301 growth cycle long, the defect that cell concentration is few.
Second aspect, the invention provides the preparation method of immobilization sulphur alkali vibrios as described in relation to the first aspect, this preparation method comprises:
At NaHCO
3in buffered soln, make Fe
3o
4magnetic nanoparticle fully contacts with addicted to salt basophilic sulphur alkali vibrios ThioalkalivibrioversutusD301 (CGMCCNo.8497) and obtains.
In above-mentioned preparation method, as preferably, described NaHCO
3the concentration of buffered soln is 0.1 ~ 1.0M, is preferably 0.3 ~ 0.8M, is more preferably 0.5M; Its pH value 7.0 ~ 12.0, is preferably 9.0 ~ 11.5, is more preferably 9.2.
As preferably, described Fe
3o
4magnetic nanoparticle is Fe
3o
4superparamagnetic nano particle;
Preferably, described Fe
3o
4the diameter of magnetic nanoparticle is 10-50nm, is preferably 10 ~ 20nm;
Preferably, described Fe
3o
4magnetic nanoparticle adopts coprecipitation method to obtain.
As preferably, described Fe
3o
4the weight ratio of the dry cell weight of superparamagnetic nano particle and sulphur alkali vibrios is 1:(20 ~ 400), be preferably 1:(100 ~ 200), be more preferably 1:100.
As preferably, above-mentioned preparation method also comprise by obtain based on Fe
3o
4the immobilization sulphur alkali vibrios of superparamagnetic nano particle carries out the step be separated by externally-applied magnetic field;
Further preferably, permanent magnetic field or the electromagnetic field of described externally-applied magnetic field to be magneticstrength be 0 ~ 6000 oersted.
In a specific embodiment, the preparation method of immobilization sulphur alkali vibrios as described in relation to the first aspect comprises the steps:
(1) Fe
3o
4the preparation of superparamagnetic nano particle:
By Fe in the 1L stirring reactor filling 400mL distilled water
3+: Fe
2+the ratio of amount of substance be 2: 1 ratio add iron trichloride and iron protochloride, be warmed up to 90 DEG C under nitrogen protection, impouring excessive concentrated ammonia solution, continue constant temperature 30min; Be cooled to room temperature, after product is separated with magnet, repeatedly clean through deionized water, add deionized water, making concentration is 20 ~ 150mg/L particle-liquid, stores for future use at 4 DEG C;
The reaction principle of this step is: 2Fe
3++ Fe
2++ 8OH
-→ Fe
3o
4+ 4H
2o.
(2) addicted to the cultivation of salt basophilic sulphur alkali vibrios ThioalkalivibrioversutusD301 (CGMCCNo.8497):
1mL is drawn in the glycerol stocks liquid of the bacterial strain ThioalkalivibrioversutusD301 (CGMCCNo.8497) be separated to from this Inner Mongol, laboratory salt alkali lake, be inoculated in the liquid nutrient medium needed for the cultivation of this bacterium, at 30 DEG C, in the shaking table of 180rpm, cultivate 8 ~ 12h.Then the bacterium liquid of 2mL is inoculated in the aforesaid liquid synthetic medium of 200mL, is placed in 30 DEG C and cultivates constant-temperature table cultivation 12 ~ 18h.By cultured inoculum at 4 DEG C, 7000rpm, centrifugal 10min, collect thalline and use 1.0M, NaCl solution washs 3 times, is then resuspended in the NaCl solution of 1.0M by thalline, and being configured to bacterial concentration is 4 ~ 5 × 10
10the bacteria suspension of/mL.
Described liquid nutrient medium composition: NaHCO
30.7mol/L, NaOH0.125mol/L, K
2hPO
43H
2o0.009mol/L, NH
4cl0.005mol/L, KNO
30.005mol/L, MgCl
26H
2o0.005mol/L, trace element (traceelements, Pfennig & Lippert, 1966) 2ml/L; PH9.5 ~ 10 after sterilizing.
(3) Fe
3o
4superparamagnetic nano particle and the immobilization addicted to salt basophilic sulphur alkali vibrios ThioalkalivibrioversutusD301 (CGMCCNo.8497):
Prepared by absorption 1mL step (2), bacterial concentration is 4 ~ 5 × 10
10the bacteria suspension of/mL joins 100mL0.3 ~ 1.0M, the NaHCO of pH9.5
3in buffered soln, shake while dropwise add the obtained exposed Fe of 1.0mL step (1)
3o
4magnetic nanoparticle (Fe
3o
4the concentration of particle is 25 ~ 125g/L), fully mix; After abundant contact, collected by externally-applied magnetic field, after 1 ~ 2min, can will compose bacterium (the i.e. Fe of the present invention of magnetic completely
3o
4superparamagnetic nano particle immobilization sulphur alkali vibrios) be separated from reaction system, can immobilization efficiency be calculated.
The third aspect, the invention provides a kind of microorganism catalysis sulfur removal technology, the immobilization sulphur alkali vibrios that this technique uses the immobilization sulphur alkali vibrios described in first aspect or the preparation method described in second aspect to obtain.
As preferably, above-mentioned sulfur removal technology is at the sodium ion containing 0.2 ~ 4M, preferably 0.3 ~ 0.8M, more preferably 0.5M, pH value is 7.0 ~ 10.65, is preferably 8.5 ~ 10, is more preferably in the reaction medium of 9.5, the immobilization sulphur alkali vibrios that immobilization sulphur alkali vibrios described in first aspect or the preparation method described in second aspect are obtained fully contacts with sulfur-bearing sample to be desulfurization, to carry out desulphurization reaction.
Further preferably, described reaction medium is NaHCO
3the substratum of damping fluid or applicable described sulphur alkali vibrios;
Still more preferably, described NaHCO
3the concentration of damping fluid is 0.1 ~ 1.0M, is preferably 0.3 ~ 0.8M, is more preferably 0.5M; Its pH value is 8.5 ~ 10.0, is preferably 9.0 ~ 9.8, is more preferably 9.5;
Still more preferably, the substratum of described applicable sulphur alkali vibrios is NaHCO
30.7mol/L, NaOH0.125mol/L, K
2hPO
43H
2o0.009mol/L, NH
4cl0.005mol/L, KNO
30.005mol/L, MgCl
26H
2o0.005mol/L, micro-2ml/L; PH after its sterilizing is 9.3 ~ 10.
As preferably, above-mentioned sulfur removal technology also comprises after desulfurization completes, by externally-applied magnetic field separated and collected based on Fe
3o
4the step of the immobilization sulphur alkali vibrios of superparamagnetic nano particle;
Further preferably, permanent magnetic field or the electromagnetic field of described externally-applied magnetic field to be magneticstrength be 0 ~ 6000 oersted.
Microorganism catalysis sulfur removal technology of the present invention, desulfuration efficiency is up to more than 95%, suitable with the desulfuration efficiency of free sulphur alkali vibrios; After desulphurization reaction completes, can at NaHCO
3reuse 3-6 time in damping fluid or in bacteria culture medium, still keep higher desulfuration efficiency.
Accompanying drawing explanation
Fig. 1 is superparamagnetism Fe prepared by embodiment 1
3o
4the transmission electron microscope picture of nano particle and energy spectrogram.
Fig. 2 is superparamagnetism Fe prepared by embodiment 1
3o
4the magnetzation curve of nano particle.
Fig. 3 is superparamagnetism Fe
3o
4nano particle adsorption of immobilization cell the procedure chart be separated by external magnetic field: the fermentation culture of (a) ThioalkalivibrioversutusD301; Magnetic nanoparticle is added in (b) fermented liquid; (c) under the effect of external magnetic field, fractionation by adsorption immobilization ThioalkalivibrioversutusD301 cell.
Fig. 4 is superparamagnetism Fe
3o
4nano particle immobilized cell and free cell are at NaHCO
3desulphurizing activated comparison in buffered soln.
Fig. 5 is superparamagnetism Fe
3o
4nano particle immobilized cell is at NaHCO
3repetition desulfurization curve in buffered soln.
Fig. 6 is superparamagnetism Fe
3o
4desulphurizing activated in ordinary culture medium is compared for nano particle immobilized cell and free cell.
Fig. 7 is superparamagnetism Fe
3o
4the repetition desulfurization curve of nano particle immobilized cell in ordinary culture medium.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
Embodiment 1 superparamagnetism Fe of the present invention
3o
4the preparation of nano particle immobilized sulphur alkali vibrios
(1) Fe
3o
4the preparation of superparamagnetic nano particle:
By Fe in the 1L stirring reactor filling 400mL distilled water
3+: Fe
2+the ratio of amount of substance be 2: 1 ratio add iron trichloride and iron protochloride, be warmed up to 90 DEG C under nitrogen protection, impouring excessive concentrated ammonia solution, continue constant temperature 30min; Be cooled to room temperature, after product is separated with magnet, repeatedly clean through deionized water, add deionized water, making concentration is 20 ~ 150mg/L particle-liquid, stores for future use at 4 DEG C.
Superparamagnetism Fe prepared by this step
3o
4the transmission electron microscope picture of nano particle as shown in Figure 1, as seen from Figure 1: Fe
3o
4nano particle is spherical in shape, and its median size is between 10 ~ 20nm.
Theoretical according to superparamagnetism, when the size of magnetic-particle reduces, in order to make it be in minimum energy state, the number of its domain wall also will reduce, and even becomes the single domain particle not having inner domain wall.If the size of single domain particle is further reduced to lower than a certain critical size Dp, when without foreign field (H=0), single domain particle in system can be less than thermal fluctuation energy due to incorgruous and make direction of magnetization stochastic distribution, and total magnetization intensity M increases rapidly, until reach capacity; Thus there is superparamagnetism phenomenon, wherein, Dp is referred to as superparamagnetism critical size.Magnetic Fe prepared by above-mentioned steps
3o
4from transmission electron microscope picture, grain diameter can confirm that its particle diameter is less than single domain superparamagnetism Fe
3o
4the theoretical critical fire area dimension D p (25nm) of particle, therefore, can tentatively judge this Fe
3o
4magnetic nanoparticle has superparamagnetism feature.
Superparamagnetism Fe prepared by this step
3o
4the magnetzation curve of nano particle as shown in Figure 2, as seen from Figure 2, Fe
3o
4the magnetzation curve of nano particle is without hysteresis, and when externally-applied magnetic field H=0, residual magnetization M=0, coercive force He=0, has superparamagnetism.Fe
3o
4the specific saturation magnetization (as) of particle is 73.985emu/g, uses Fe
3o
4the specific saturation magnetization of the cell of embed particles is 55.108emu/g, in the suspension liquid of magnetic-particle immobilization bacterium, is easy to use common permanent magnet it to be separated fast.
(2) addicted to the cultivation of salt basophilic sulphur alkali vibrios ThioalkalivibrioversutusD301 (CGMCCNo.8497):
1mL is drawn in the glycerol stocks liquid of the bacterial strain ThioalkalivibrioversutusD301 (CGMCCNo.8497) be separated to from this Inner Mongol, laboratory salt alkali lake, be inoculated in the liquid nutrient medium needed for the cultivation of this bacterium, at 30 DEG C, in the shaking table of 180rpm, cultivate 8 ~ 12h.Then the bacterium liquid of 2mL is inoculated in the aforesaid liquid synthetic medium of 200mL, is placed in 30 DEG C and cultivates constant-temperature table cultivation 12 ~ 18h.By cultured inoculum at 4 DEG C, 7000rpm, centrifugal 10min, collect thalline and use 1.0M, NaCl solution washs 3 times, is then resuspended in the NaCl solution of 1.0M by thalline, and being configured to bacterial concentration is 4 ~ 5 × 10
10the bacteria suspension of/mL.
Liquid nutrient medium forms: NaHCO
30.7mol/L, NaOH0.125mol/L, K
2hPO
43H
2o0.009mol/L, NH
4cl0.005mol/L, KNO
30.005mol/L, MgCl
26H
2o0.005mol/L, trace element (traceelements, Pfennig & Lippert, 1966) 2ml/L; PH9.5 ~ 10 after sterilizing.
(3) Fe
3o
4superparamagnetic nano particle and the immobilization addicted to salt basophilic sulphur alkali vibrios ThioalkalivibrioversutusD301 (CGMCCNo.8497):
Prepared by absorption 1mL step (2), bacterial concentration is 4 ~ 5 × 10
10the bacteria suspension of/mL joins 100mL0.5M, the NaHCO of pH9.5
3in buffered soln, shake while dropwise add the obtained exposed Fe of 1.0mL step (1)
3o
4magnetic nanoparticle (Fe
3o
4the concentration of particle is 25 ~ 125g/L), fully mix; After abundant contact, collected by externally-applied magnetic field, after 1 ~ 2min, can will compose bacterium (the i.e. Fe of the present invention of magnetic completely
3o
4superparamagnetic nano particle immobilization sulphur alkali vibrios) be separated from reaction system, can immobilization efficiency be calculated.
Use superparamagnetism Fe
3o
4as shown in Figure 3, in figure 3, (a) shows the fermentation culture of sulphur alkali vibrios ThioalkalivibrioversutusD301 for nano particle adsorption of immobilization sulphur alkali vibrios cell the procedure chart be separated by external magnetic field; Magnetic nanoparticle is added in (b) display fermented liquid; C () is presented at the effect of external magnetic field under, fractionation by adsorption immobilization ThioalkalivibrioversutusD301 cell.
Embodiment 2 superparamagnetism Fe of the present invention
3o
4nano particle immobilized sulphur alkali vibrios is at NaHCO
3desulfurization performance in buffered soln
Respectively by magnetic Fe prepared by embodiment 1
3o
4nano particle immobilized sulphur alkali vibrios cell 1mL (2 ~ 3 × 10
8individual cell/mL) and free cell suspension 0.5mL (2 ~ 3 × 10
8individual cell/mL) join the NaHCO of 50mL containing Sulfothiorine
3in buffered soln (0.5M, pH9.5), carry out desulphurization reaction.At set intervals, from reaction solution, draw a certain amount of absorption liquid, with the content of ion chromatography thiosulfate anion and sulfate radical, calculate the output of elemental sulfur.
Magnetic Fe of the present invention
3o
4the desulphurizing activated result of nano particle immobilized sulphur alkali vibrios and free cell as shown in Figure 4.As seen from Figure 4, magnetic Fe of the present invention
3o
4nano particle immobilized sulphur alkali vibrios desulphurizing activated very high, its desulfurization curve is similar to free cell, and in 24h, 3600mg/L thiosulfate anion all can be oxidized by the two, generates about 2300mg/L sulfate radical and 1300mg/L elemental sulfur.
Embodiment 3 superparamagnetism Fe of the present invention
3o
4nano particle immobilized sulphur alkali vibrios is at NaHCO
3performance is recycled in buffered soln
After the desulphurization reaction of above-described embodiment 2 completes, under the effect of externally-applied magnetic field, separated and collected magnetic Fe
3o
4nano particle immobilized cell; The magnetic Fe reclaimed
3o
4the above-mentioned NaHCO containing Sulfothiorine is rejoined in nano particle immobilized cell
3buffered soln (0.5M, pH9.5), carries out repetition desulphurization reaction.After each rhythmic reaction completes, centrifugal and externally-applied magnetic field is used to collect free thalline and magnetic Fe
3o
4nano particle immobilized thalline, and be used as next step reaction.Recycling to dissociate thalline and magnetic Fe by comparison
3o
4the desulfurization degree of nano particle immobilized thalline obtains.
Magnetic Fe
3o
4the repetition desulfurization curve of nano particle immobilized somatic cells is shown in Fig. 5, as seen from Figure 5, and magnetic Fe of the present invention
3o
4nano particle immobilized sulphur alkali vibrios can reuse 3 times, after reusing 3 times, still keep higher desulfurization rate.
Embodiment 4 superparamagnetism Fe of the present invention
3o
4the desulfurization performance of nano particle immobilized sulphur alkali vibrios in ordinary culture medium
By superparamagnetism Fe prepared by embodiment 1
3o
4nano particle immobilized sulphur alkali vibrios cell 2mL (2 ~ 3 × 10
8individual cell/mL) and free cell suspension 1.0mL (2 ~ 3 × 10
8individual cell/mL) (substratum consists of: NaHCO containing the ordinary culture medium of Sulfothiorine to join 100mL respectively
30.7mol/L, NaOH0.125mol/L, K
2hPO
43H
2o0.009mol/L, NH
4cl0.005mol/L, KNO
30.005mol/L, MgCl
26H
2o0.005mol/L, trace element (traceelements, Pfennig & Lippert, 1966) 2ml/L; PH9.3 ~ 10 after sterilizing) in, carry out desulphurization reaction.At set intervals, from reaction solution, draw a certain amount of absorption liquid, with the content of ion chromatography thiosulfate anion and sulfate radical, calculate the output of elemental sulfur.
Described magnetic Fe
3o
4nano particle immobilized sulphur alkali vibrios and free cell above-mentioned ordinary culture medium China desulphurizing activated result as shown in Figure 6.As seen from Figure 6, magnetic Fe of the present invention
3o
4nano particle immobilized sulphur alkali vibrios desulphurizing activated very high, its desulfurization curve is similar to free cell, and in 24h, 8000mg/L thiosulfate anion all can be oxidized by the two, generates about 3500 ~ 4000mg/L sulfate radical and 3300mg/L elemental sulfur.
Embodiment 5 superparamagnetism Fe of the present invention
3o
4nano particle immobilized sulphur alkali vibrios recycles performance in ordinary culture medium
After the desulphurization reaction of above-described embodiment 4 completes, under the effect of externally-applied magnetic field, separated and collected magnetic Fe
3o
4nano particle immobilized cell; By the magnetic Fe reclaimed
3o
4nano particle immobilized cell adds the above-mentioned ordinary culture medium containing Sulfothiorine, carries out repetition desulphurization reaction.After each rhythmic reaction completes, centrifugal and externally-applied magnetic field is used to collect free thalline and magnetic Fe
3o
4nano particle immobilized thalline, and be used as next step reaction.Recycling to dissociate thalline and magnetic Fe by comparison
3o
4the desulfurization degree of nano particle immobilized thalline obtains.
Magnetic Fe
3o
4the repetition desulfurization curve of nano particle immobilized somatic cells is shown in Fig. 7, as seen from Figure 7, and magnetic Fe of the present invention
3o
4nano particle immobilized sulphur alkali vibrios can reuse more than 6 times, after reusing 6 times, still keep higher desulfurization rate.
Applicant states, the present invention illustrates detailed features of the present invention and method detailed by above-described embodiment, but the present invention is not limited to above-mentioned detailed features and method detailed, namely do not mean that the present invention must rely on above-mentioned detailed features and method detailed could be implemented.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, concrete way choice etc. that the present invention selects component, all drops within protection scope of the present invention and open scope.
Claims (10)
1. one kind based on Fe
3o
4the immobilization sulphur alkali vibrios of magnetic nanoparticle, is characterized in that, by making Fe
3o
4magnetic nanoparticle is adsorbed on addicted to the cell surface of salt basophilic sulphur alkali vibrios ThioalkalivibrioversutusD301 (CGMCCNo.8497) and obtains.
2. immobilization sulphur alkali vibrios as claimed in claim 1, is characterized in that, described Fe
3o
4magnetic nanoparticle is Fe
3o
4superparamagnetic nano particle;
Preferably, described Fe
3o
4the diameter of magnetic nanoparticle is 10-50nm, is preferably 10 ~ 20nm;
Preferably, described Fe
3o
4magnetic nanoparticle adopts coprecipitation method to obtain.
3. the preparation method of immobilization sulphur alkali vibrios as claimed in claim 1 or 2, is characterized in that, comprising:
At NaHCO
3in buffered soln, make Fe
3o
4magnetic nanoparticle fully contacts with addicted to salt basophilic sulphur alkali vibrios ThioalkalivibrioversutusD301 (CGMCCNo.8497) and obtains.
4. preparation method according to claim 3, is characterized in that, described NaHCO
3the concentration of buffered soln is 0.1 ~ 1.0M, is preferably 0.3 ~ 0.8M, is more preferably 0.5M; Its pH value is 7.0 ~ 12.0, is preferably 9.0 ~ 11.5, is more preferably 9.2;
Preferably, described Fe
3o
4magnetic nanoparticle is Fe
3o
4superparamagnetic nano particle;
Preferably, described Fe
3o
4the diameter of magnetic nanoparticle is 10-50nm, is preferably 10 ~ 20nm;
Preferably, described Fe
3o
4magnetic nanoparticle adopts coprecipitation method to obtain.
5. the preparation method as described in claim 3 or 4, is characterized in that, described Fe
3o
4the weight ratio of the dry cell weight of superparamagnetic nano particle and sulphur alkali vibrios is 1:(20 ~ 400), be preferably 1:(100 ~ 200), be more preferably 1:100.
6. the preparation method according to any one of claim 3-5, is characterized in that, also comprise by obtain based on Fe
3o
4the immobilization sulphur alkali vibrios of superparamagnetic nano particle carries out the step be separated by externally-applied magnetic field;
Preferably, permanent magnetic field or the electromagnetic field of described externally-applied magnetic field to be magneticstrength be 0 ~ 6000 oersted.
7. a microorganism catalysis sulfur removal technology, is characterized in that, the immobilization sulphur alkali vibrios that this technique uses the immobilization sulphur alkali vibrios described in claim 1 or 2 or obtained by the preparation method described in any one of claim 3-6.
8. sulfur removal technology as claimed in claim 7, it is characterized in that, at the sodium ion containing 0.2 ~ 4M, preferably 0.3-0.8M, more preferably 0.5M, pH value is 7.0 ~ 10.65, is preferably 8.5 ~ 10, is more preferably in the reaction medium of 9.5, immobilization sulphur alkali vibrios described in claim 1 or 2 or the immobilization sulphur alkali vibrios that obtained by the preparation method described in any one of claim 3-6 are fully contacted with sulfur-bearing sample to be desulfurization, to carry out desulphurization reaction.
9. sulfur removal technology as claimed in claim 8, it is characterized in that, described reaction medium is NaHCO
3the substratum of damping fluid or applicable described sulphur alkali vibrios;
Preferably, described NaHCO
3the concentration of damping fluid is 0.1 ~ 1.0M, is preferably 0.3 ~ 0.8M, is more preferably 0.5M; Its pH value is 8.5 ~ 10.0, is preferably 9.0 ~ 9.8, is more preferably 9.5;
Preferably, the described substratum being applicable to described sulphur alkali vibrios is NaHCO
30.7mol/L, NaOH0.125mol/L, K
2hPO
43H
2o0.009mol/L, NH
4cl0.005mol/L, KNO
30.005mol/L, MgCl
26H
2o0.005mol/L, micro-2ml/L; PH after its sterilizing is 9.3 ~ 10.
10. the sulfur removal technology according to any one of claim 7-9, is characterized in that, also comprises after desulfurization completes, by externally-applied magnetic field separated and collected based on Fe
3o
4the step of the immobilization sulphur alkali vibrios of superparamagnetic nano particle;
Preferably, permanent magnetic field or the electromagnetic field of described externally-applied magnetic field to be magneticstrength be 0 ~ 6000 oersted.
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