CN109777756A - A kind of microbial inoculum and the application of simultaneous removing hydrogen sulfide and ammonia - Google Patents
A kind of microbial inoculum and the application of simultaneous removing hydrogen sulfide and ammonia Download PDFInfo
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- CN109777756A CN109777756A CN201910112018.3A CN201910112018A CN109777756A CN 109777756 A CN109777756 A CN 109777756A CN 201910112018 A CN201910112018 A CN 201910112018A CN 109777756 A CN109777756 A CN 109777756A
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Abstract
The present invention relates to microbial inoculum and the applications of a kind of simultaneous removing hydrogen sulfide and ammonia, can be used for utilization of waste as resource field and field of environment protection.Microbial inoculum includes ferrous oxide hook end spirillum and Thiobacillus thioxidans.The present invention can be by H by the effect of desulfurization deamination composite bacteria agent2The S of S2‑It is oxidized to SO4 2‑；NH3With the H in acid medium+In conjunction with formation NH4 +。(NH4)2SO4It is one of microbial inoculum culture medium main component, needed for being used for growth and breeding by composite bacteria agent, to reach simultaneous removing H2S and NH3Purpose.H2S removal efficiency is up to 99.2%~99.5%, NH3Removal efficiency up to 95.2%~99.4% and microbial inoculum it is reusable.
Description
Technical field
The present invention relates to a kind of simultaneous removing hydrogen sulfide (H2S) with ammonia (NH3) microbial inoculum and application.Specifically with
Ferrous oxide hooks end spirillum (Leptospirillum ferrooxidans) and Thiobacillus thioxidans (Thiobacillus
It thiooxidans) is raw material simultaneous removing H2S and NH3Microbial inoculum and application, belong to waste resource technology field and environment be micro-
Biological field.
Background technique
The main component for cultivating exhaust gas and sewage treatment plant's exhaust gas is H2S and NH3, H2S and NH3Biological mucosa can be corroded, lured
Respiratory disease is sent out, the immunity degradation of living organism is also resulted in；Lead to the super nutrient laden of soil, causes environmental pollution.
H2S and NH3Processing method has physical method (Physical Absorption hair, microwave method, active carbon adsorption, membrane separation process), changes
Method (Claus method, liquid phase catalytic oxidation) and bioanalysis.There are energy consumption height, at high cost, biology for physics and chemical method
The problem of method power output effect difference.Therefore, it cultivates exhaust gas and the processing problem of sewage treatment plant's exhaust gas is paid much attention to.Mesh
Before, bioanalysis also in developing stage, have at low cost, pollution less, stably and controllable service condition be its clear advantage, still
There are still H2S removal efficiency, NH3The problems such as removal efficiency is generally relatively low.
Autunezite (chemical formula KFe3(SO4)2(OH)6) it is a kind of widely used material.Such as: it can be used as and grind
Material is ground, grinding industry is applied to after processing；It is a kind of ochre yellow natural dye again, is applied to drawing and ancient architecture, ancient times
The reparation of implements；Autunezite is also widely used for smelting in the metal industries such as zinc, nickel, cobalt except iron.
Summary of the invention
In view of the problems of prior art, the present invention provides a kind of simultaneous removing H2S and NH3Microbial inoculum and application.This
Invention is by the mixing of two kinds of microorganisms of ferrous oxide hook end spirillum and Thiobacillus thioxidans and applies, and overcomes farm
With the exhaust-gas treatment problem of sewage treatment plant, and the application direction of the microbial inoculum has been expanded.The microbial inoculum can be with simultaneous removing H2S and
NH3, H2S removal efficiency is up to 99.2%~99.5%, NH3Removal efficiency is up to 95.2%~99.4%.With H2S removal efficiency height, NH3
Removal efficiency is high, and it is environmentally friendly, there is no secondary pollution generation, the advantages that microbial inoculum is reusable.
The technical scheme to solve the above technical problems is that
A kind of simultaneous removing hydrogen sulfide (H2S) with ammonia (NH3) microbial inoculum, including ferrous oxide hook end spirillum and oxidation
Sulphur Thiobacillus.
The beneficial effects of the present invention are: ferrous oxide hook end spirillum is with Oxidation of Fe2+, elemental sulfur, reducible sulfur compound etc.
Lower valency member usually grows obtained from body cell and is metabolized required energy, with NH4+For nitrogen source, with the CO in air2For carbon
Source.Thiobacillus thioxidans to obtain own cells growth and is metabolized required energy with the sulfide of oxidizing simple substance sulphur or reduction-state
Amount, with NH4+For nitrogen source, with CO in air2For carbon source.Ferrous oxide hook end spirillum is by H in composite bacteria agent sweetening process2S
It is oxidized to elemental sulfur, Thiobacillus thioxidans is by H2S or elemental sulfur are oxidized to SO4 2-, and NH3Then with H in culture medium2SO4Occur anti-
(NH should be generated4)2SO4, (NH4)2SO4It is used for growth and the metabolism institute of ferrous oxide hook end spirillum and Thiobacillus thioxidans
It needs.By this composite bacteria agent, H can be absorbed with circulation synchronous2S and NH3, and its product elemental sulfur is easily recycled, (NH4)2SO4
It is composite bacteria agent culture medium.Microbial inoculum of the invention is compounded using ferrous oxide hook end spirillum and Thiobacillus thioxidans,
With H2S removal efficiency height, NH3Removal efficiency is high, and it is environmentally friendly, there is no secondary pollution generation, microbial inoculum reusable etc. excellent
Point.
Based on the above technical solution, the present invention can also be improved as follows.
Further, it is CCTCC AB 206158, CCTCC AB that the ferrous oxide hook end spirillum, which is selected from deposit number,
206159、CCTCC AB 206160、CCTCC AB 206161、CCTCC AB 206162、CCTCC AB 206163、CCTCC
One of bacterial strain of AB 206164, CCTCC AB 207036, CCTCC AB 207037, CCTCC AB 207038 is several
Kind.
Having the beneficial effect that using the above scheme can be mentioned further using the ferrous oxide hook end spirillum of mentioned kind
High H2S removal efficiency and NH3Removal efficiency.
Further, it is CCTCC AB 206195, CCTCC AB 206196, CCTCC that Thiobacillus thioxidans, which is selected from deposit number,
One or more of the bacterial strain of AB 206197.
Having the beneficial effect that using the above scheme can be further improved H using the Thiobacillus thioxidans of mentioned kind2S
Removal efficiency and NH3Removal efficiency.
Preferably, the ratio of the thalline quantity of ferrous oxide hook end spirillum and Thiobacillus thioxidans is (1-3): (3-1).
H can be further improved using said ratio2S removal efficiency and NH3Removal efficiency, H2S removal efficiency is up to 99.2%~99.5%, NH3
Removal efficiency is up to 95.2%~99.4%.Further, the thalline quantity of ferrous oxide hook end spirillum and Thiobacillus thioxidans
Ratio is (35-45): (55-65).Optimal, when the ratio of the thalline quantity of ferrous oxide hook end spirillum and Thiobacillus thioxidans
When example is 2:3, H2S removal efficiency and NH3Removal efficiency can achieve 99% or more.
The present invention also provides application of the above-mentioned microbial inoculum in desulfurization and/or deamination.Specifically, above-mentioned microbial inoculum is in removing H2S
And/or NH3In application.
Microbial inoculum of the present invention can be used for the useless of the places such as farm, sewage treatment plant (but being not limited only to above-mentioned place)
Desulfurization and deamination are handled.
The present invention also provides above-mentioned microbial inoculums in preparation KFe3(SO4)2(OH)6、H3OFe3(SO4)2(OH)6And/or NH4Fe3
(SO4)2(OH)6In application.
Having the beneficial effect that using the above scheme
Microbial inoculum of the present invention in sweetening process ferrous oxide hook end spirillum by H2S is oxidized to elemental sulfur, sulfur oxide
Thiobacillus is by H2S or elemental sulfur are oxidized to SO4 2-, and NH3Then with H in culture medium2SO4React generation (NH4)2SO4, (NH4)2SO4It is used for needed for the growth and metabolism of ferrous oxide hook end spirillum and Thiobacillus thioxidans.Extra NH in system4+With
SO4 2-Autunezite (chemical formula KFe is then generated under the action of ferrous oxide hook end spirillum3(SO4)2(OH)6) precipitating.It is yellow
The specific reaction equation of krausite is as follows:
4Fe2++4H++O2→4Fe3++2H2O
Fe3++H2O→FeOH2++H+
FeOH2++H2O→Fe(OH)2 ++H+
2Fe3++2H2O→Fe2(OH)2 4++4H+
3Fe(OH)3+4SO4 2-+3Fe3++4H2O+2M+→2MFe3(SO4)2(OH)6+3H+
Wherein, M+It can be K+、H3O+Or NH4+。
The present invention also provides the preparation methods of above-mentioned microbial inoculum, comprising the following steps: by ferrous oxide hook end spirillum and oxygen
Change sulphur Thiobacillus to be cultivated respectively to logarithmic phase, obtains ferrous oxide hook end spirillum bacterium solution and Thiobacillus thioxidans bacterium solution, later
The ferrous oxide hook end spirillum bacterium solution and Thiobacillus thioxidans bacterium solution of logarithmic phase are mixed, microbial inoculum is made.
Having the beneficial effect that using the above scheme has H by microbial inoculum prepared by the above method2S removal efficiency height, NH3Removing
Rate is high, and it is environmentally friendly, there is no secondary pollution generation, the advantages that microbial inoculum is reusable.
Preferably, ferrous oxide hook end spirillum bacterium solution and Thiobacillus thioxidans bacterium solution are with volume ratio (1~3): (3~1)
Mixing, when using aforementioned proportion, H2S removal efficiency and NH3Removal efficiency can achieve 92% or more.Optimal, ferrous oxide hook
Hold spirillum bacterium solution and Thiobacillus thioxidans bacterium solution with volume ratio 2:3 mixing, when using aforementioned proportion, H2S removal efficiency and NH3
Removal efficiency can achieve 99% or more.
Further, the inoculative proportion of ferrous oxide hook end spirillum bacterium solution is volume ratio 5%~10%, Thiobacillus thioxidans
The inoculative proportion of bacterium solution is volume ratio 5%~10%, and the cultivation temperature of ferrous oxide hook end spirillum and Thiobacillus thioxidans is
28~32 DEG C.
Specifically, ferrous oxide hook end spiral bacterium culture medium includes the following components: (NH of 0.24~0.30g/L4)2SO4,
The K of the KCl of 0.1~1.0g/L, 0.50~5.0g/L2HPO4, the MgSO of 0.50~5.0g/L4·7H2O, 0.01~0.1g/L's
Ca(NO3)2, the FeSO of 30~50g/L4·7H2O, pH are 1.8~2.2, and solvent is water.
Thiobacillus thioxidans culture medium includes the following components: (NH of 0.24~0.30g/L4)2SO4, 0.1~1.0g/L's
The K of KCl, 0.50~5.0g/L2HPO4, the MgSO of 0.50~5.0g/L4·7H2Ca (the NO of O, 0.01~0.1g/L3)2, 5~
The Na of 10g/L2S2O3, pH is 2.0~3.0, and solvent is water.
Using the above scheme have the beneficial effect that suitable inoculative proportion be conducive to bacterium to be rapidly achieved bacterium living beings living
Property highest logarithmic phase, avoid the problem that bacterial reproduction is excessively slow or breeding is excessive；Suitable fermentation temperature is conducive to thallus
Growth cultivates to logarithmic phase and is conducive to improve bacterium solution to the absorption efficiency of exhaust gas.
A kind of preparation method of the fermentation liquid containing above-mentioned microbial inoculum, comprising the following steps: microbial inoculum is inoculated into culture medium,
Fermented and cultured obtains the fermentation liquid containing above-mentioned microbial inoculum.
Having the beneficial effect that using the above scheme has H by fermentation liquid prepared by the above method2S removal efficiency height, NH3It is de-
Except rate height, and it is environmentally friendly, there is no secondary pollution generation, the advantages that microbial inoculum is reusable.
Further, the inoculative proportion of microbial inoculum is volume ratio 5%~10%, and cultivation temperature is 28~32 DEG C, culture to logarithm
Phase.
Culture medium for microbial inoculum inoculation includes the following components: (NH of 0.10~0.24g/L4)2SO4, 0.1~1.0g/L
KCl, the K of 0.50~5.0g/L2HPO4, the MgSO of 0.50~5.0g/L4·7H2Ca (the NO of O, 0.01~0.1g/L3)2, 10
The FeSO of~30g/L4·7H2The Na of O, 1~5g/L2S2O3, pH is 1.8~2.2, and solvent is water.
Having the beneficial effect that using the above scheme can be further improved H2S removal efficiency height, NH3Removal efficiency is high.
The present invention also provides the methods for using above-mentioned microbial inoculum desulfurization and/or deamination, comprising the following steps: (1) connects microbial inoculum
For kind into culture medium, fermented and cultured obtains the fermentation liquid containing above-mentioned microbial inoculum；(2) H will be contained2S and/or NH3Exhaust gas be passed through
In the fermentation liquid of above-mentioned microbial inoculum, removing H is carried out2S and/or NH3Processing.
Having the beneficial effect that using the above scheme has H using the above method2S removal efficiency height, NH3Removal efficiency is high, and
It is environmentally friendly, there is no secondary pollution generation, the advantages that microbial inoculum is reusable.
The present invention also provides a kind of methods for preparing autunezite using above-mentioned microbial inoculum, comprising the following steps:
(1) microbial inoculum is inoculated into containing K2SO4Desulfurization deamination composite bacteria agent culture medium in, fermented and cultured obtains fermentation liquid
And precipitating；
(2) precipitating that step (1) obtains is impregnated with hydrochloric acid solution, is centrifuged, collect precipitating later；
(3) washing of precipitate, the filtering collected step (2), by filter residue and drying, obtain autunezite.
Having the beneficial effect that using the above scheme prepares autunezite with environmental-friendly, safety using the above method
Height, it is without secondary pollution, it is at low cost the advantages that.
Specifically, the inoculative proportion of microbial inoculum is volume ratio 5%~10%, the time of fermented and cultured is 48h, fermented and cultured temperature
Degree is 28~32 DEG C, K2SO4Concentration be 10g/L.
The formula of desulfurization deamination composite bacteria agent culture medium can be with are as follows: (the NH of 0.10~0.24g/L4)2SO4, 0.1~1.0g/
The K of the KCl of L, 0.50~5.0g/L2HPO4, the MgSO of 0.50~5.0g/L4·7H2Ca (the NO of O, 0.01~0.1g/L3)2, 10
The FeSO of~30g/L4·7H2The Na of O, 1~5g/L2S2O3, pH is 1.8~2.2, and solvent is water.
Having the beneficial effect that using the above scheme is matched using above-mentioned condition of culture and desulfurization deamination composite bacteria agent culture medium
Side is conducive to improve the yield of autunezite.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
The present invention provides a kind of simultaneous removing H2S and NH3Composite bacteria agent, specific preparation method can be with are as follows: by ferrous oxide
Hook end spirillum and Thiobacillus thioxidans pass through adaptability culture, press ferrous oxide hook end spirillum and oxygen after continuous expansion culture
Change sulphur Thiobacillus to mix with the ratio of logarithmic phase bacterium solution volume ratio 2:3, obtaining mix bacterium agent, (thallus total concentration is in mix bacterium agent
1×107~8 × 107cells/ml)。
The ferrous oxide hook end spirillum can choose one or more of the bacterial strain of following 10 kinds of deposit numbers, and 10
The bacterial strain of kind deposit number is respectively as follows: CCTCC AB 206158, CCTCC AB 206159, CCTCC AB 206160, CCTCC AB
206161、CCTCC AB 206162、CCTCC AB 206163、CCTCC AB 206164、CCTCC AB 207036、CCTCC
AB 207037 and CCTCC AB 207038.Above-mentioned bacterial strains are deposited in China typical culture collection center (CCTCC), the public
Above-mentioned bacterial strains can be obtained by way of purchase.
Thiobacillus thioxidans can choose one or more of the bacterial strain of following 3 kinds of deposit numbers, the bacterial strain of 3 kinds of deposit numbers
It is respectively as follows: CCTCC AB 206195, CCTCC AB 206196 and CCTCC AB 206197.Above-mentioned bacterial strains are deposited in China
Type Tissue Collection (CCTCC), the public can obtain above-mentioned bacterial strains by way of purchase.
Two kinds of bacterium that composite bacteria agent of the present invention is related to are respectively ferrous oxide hook end spirillum, Thiobacillus thioxidans.It is making
When standby above-mentioned microbial inoculum, the culture medium being related to is included the following three types:
Ferrous oxide hook end spiral bacterium culture medium includes the following components: (NH of 0.24~0.30g/L4)2SO4, 0.1~
The K of the KC l, 0.50~5.0g/L of 1.0g/L2HPO4, the MgSO of 0.50~5.0g/L4·7H2The Ca of O, 0.01~0.1g/L
(NO3)2, the FeSO of 30~50g/L4·7H2O, pH are 1.8~2.2, and solvent is water.
Thiobacillus thioxidans culture medium includes the following components: (NH of 0.24~0.30g/L4)2SO4, 0.1~1.0g/L's
The K of KCl, 0.50~5.0g/L2HPO4, the MgSO of 0.50~5.0g/L4·7H2Ca (the NO of O, 0.01~0.1g/L3)2, 5~
The Na of 10g/L2S2O3, pH is 2.0~3.0, and solvent is water.
Desulfurization deamination composite bacteria agent culture medium (referred to as mix bacterium agent culture medium) includes following components: 0.10~0.24g/
(the NH of L4)2SO4, the K of the KCl of 0.1~1.0g/L, 0.50~5.0g/L2HPO4, the MgSO of 0.50~5.0g/L4·7H2O,
Ca (the NO of 0.01~0.1g/L3)2, the FeSO of 10~30g/L4·7H2The Na of O, 1~5g/L2S2O3, pH is 1.8~2.2, molten
Agent is water.
Microbial inoculum can be prepared by method in detail below:
Ferrous oxide hook end spirillum and Thiobacillus thioxidans activation culture:
The culture of ferrous oxide hook end spirillum: by the ferrous oxide hook end spirillum of logarithmic phase with 5%~10% (v/v)
The bacterium amount that connects be inoculated in ferrous oxide hook end spiral bacterium culture medium respectively, 28~32 DEG C, ferment in the shaking table of 100~120rpm
Culture.Obtain the ferrous oxide hook end spirillum bacterium solution of logarithmic phase.Using logarithmic phase bacteria solution active highest, be conducive to connect next time
Kind；Composite bacteria agent is facilitated to match in proportion.
The culture of Thiobacillus thioxidans: the Thiobacillus thioxidans of logarithmic phase is connect into bacterium amount difference with 5%~10% (v/v)
It is inoculated in Thiobacillus thioxidans culture medium, 28~32 DEG C, fermented and cultured in the shaking table of 100~120rpm.Obtain logarithmic phase
Thiobacillus thioxidans bacterium solution.Logarithmic phase bacteria solution active highest, is conducive to next inoculation；Composite microbial system is facilitated to match in proportion.
Optimize the proportion of desulfurization deamination composite bacteria agent: by the logarithmic phase of ferrous oxide hook end spirillum and Thiobacillus thioxidans
Bacterium solution in bacterium solution volume ratio 1:0,1:1,1:2,2:3,3:2,2:1,0:1 ratio mixing match, successively obtains ferrous oxide respectively
The thalline quantity of hook end spirillum and Thiobacillus thioxidans than be respectively 1:0,1:1,1:2,2:3,3:2,2:1,0:1 microbial inoculum,
It is inoculated in the mix bacterium agent culture medium of 3000ml with the inoculum concentration of 5%~10% (v/v, i.e. microbial inoculum and culture volume ratio),
28~32 DEG C, 100~120rpm shaking table culture 40h obtains fermentation liquid.
Detect the desulfurization deamination effect of composite bacteria agent: with H2S and NH3For raw material simulated exhaust, the exhaust gas of simulation is passed through hair
In zymotic fluid, draft speed is 100~200ml/min, collects tail gas and collects after ventilation 2 hours and detect H in whole tail gas2S
With NH3Content calculates desulfurization deamination effect.It is preferred that going out the composite bacteria agent ratio of optimal desulfurization deamination effect.
The by-product that the processing tail gas of composite bacteria agent generates is collected, concrete operations can be with are as follows:
Composite bacteria agent absorbs H2S and NH3Afterwards, after when bacterium solution culture about 48 is small, byproduct precipitate can be generated, is sunk after standing
Drop can be located at the bottom of container, will precipitate with after 10~12h of HCl soaking at room temperature of 1~1.5M, be centrifuged 10min through 10000rpm,
Precipitating is collected, constant weight is dried under vacuum to, obtains yellow KFe3(SO4)2(OH)6、H3OFe3(SO4)2(OH)6And NH4Fe3(SO4)2(OH)6
Solid mixture.
Prepare autunezite preparation method the following steps are included:
(1) composite bacteria agent is inoculated in 3000ml desulfurization deamination composite bacteria agent culture with the inoculum concentration of 5%~10% (v/v)
In base, desulfurization deamination composite bacteria agent culture medium is added with the K of 10g/L2SO4, sub- after 100~120rpm, 28~32 DEG C of culture 48h
Iron oxygenation efficiency reaches 80%~90%；(2) byproduct precipitate that can be generated at this time can be deposited in the bottom of container after standing, will
The precipitating of generation is centrifuged 10min through 10000rpm, is collected precipitating with after 10~12h of HCl soaking at room temperature of 1~1.5M；(3) it uses
The dilute hydrochloric acid that distilled water or volume fraction are 5%~8% washs, and filtering, filter residue is dried under vacuum to constant weight, and yellow potassium iron is obtained after grinding
Alum flour end.
Embodiment 1: ferrous oxide hook end spirillum and Thiobacillus thioxidans composite bacteria agent are prepared
The culture of ferrous oxide hook end spirillum: by the ferrous oxide hook end spirillum of logarithmic phase with 5%~10% (v/v)
The bacterium amount that connects be inoculated in ferrous oxide hook end spiral bacterium culture medium respectively, 28~32 DEG C, ferment in the shaking table of 100~120rpm
Culture.Obtain the ferrous oxide hook end spirillum bacterium solution of logarithmic phase.
Ferrous oxide hook end spiral bacterium culture medium includes the following components: (NH of 0.24~0.30g/L4)2SO4, 0.1~
The K of the KCl of 1.0g/L, 0.50~5.0g/L2HPO4, the MgSO of 0.50~5.0g/L4·7H2The Ca of O, 0.01~0.1g/L
(NO3)2, the FeSO of 30~50g/L4·7H2O, pH are 1.8~2.2, and solvent is water.
The culture of Thiobacillus thioxidans: the Thiobacillus thioxidans of logarithmic phase is connect respectively with the bacterium amount that connects of 5~10% (v/v)
It plants in Thiobacillus thioxidans culture medium, 28~32 DEG C, fermented and cultured in the shaking table of 100~120rpm.Obtain the oxygen of logarithmic phase
Change sulphur Thiobacillus bacterium solution.
Thiobacillus thioxidans culture medium includes the following components: (NH of 0.24~0.30g/L4)2SO4, 0.1~1.0g/L's
The K of KCl, 0.50~5.0g/L2HPO4, the MgSO of 0.50~5.0g/L4·7H2Ca (the NO of O, 0.01~0.1g/L3)2, 5~
The Na of 10g/L2S2O3, pH is 2.0~3.0, and solvent is water.
Ferrous oxide hook end spirillum and Thiobacillus thioxidans microbial inoculum proportion: by ferrous oxide hook end spirillum and sulfur oxide
The logarithmic phase bacterium solution of Thiobacillus distinguishes 1:0,1:1,1:2,2:3,3:2,2:1,0:1 ratio mixing match by volume, successively
To the thalline quantity of ferrous oxide hook end spirillum and Thiobacillus thioxidans than be respectively 1:0,1:1,1:2,2:3,3:2,2:1,
Microbial inoculum after proportion is inoculated in the mix bacterium agent culture medium of 3000ml by the microbial inoculum of 0:1 by the inoculum concentration of 5%~10% (v/v)
In, 100~120rpm, 28~32 DEG C of cultures are spare to logarithmic phase.
Mix bacterium agent culture medium includes the following components: (NH of 0.10~0.24g/L4)2SO4, the KCl of 0.1~1.0g/L,
The K of 0.50~5.0g/L2HPO4, the MgSO of 0.50~5.0g/L4·7H2Ca (the NO of O, 0.01~0.1g/L3)2, 10~30g/L
FeSO4·7H2The Na of O, 1~5g/L2S2O3, pH is 1.8~2.2, and solvent is water.
Embodiment 1A
The culture of ferrous oxide hook end spirillum:
The deposit number of ferrous oxide hook end spirillum is specially CCTCC AB 206158.By ferrous oxide hook end spiral
Bacterium is inoculated in ferrous oxide hook end spiral bacterium culture medium with the bacterium amount that connects of 5% (v/v), and 28 DEG C, is fermented in the shaking table of 100rpm
Culture.Obtain the ferrous oxide hook end spirillum bacterium solution of logarithmic phase.
Ferrous oxide hook end spiral bacterium culture medium includes the following components: (NH of 0.24g/L4)2SO4, the KCl of 0.1g/L,
The K of 0.50g/L2HPO4, the MgSO of 0.50g/L4·7H2Ca (the NO of O, 0.01g/L3)2, the FeSO of 30g/L4·7H2O, pH are
1.8, solvent is water.
The culture of Thiobacillus thioxidans:
The deposit number of Thiobacillus thioxidans is specially CCTCC AB 206195.By Thiobacillus thioxidans with 5% (v/v)
The bacterium amount that connects be inoculated in Thiobacillus thioxidans culture medium, 28 DEG C, fermented and cultured in the shaking table of 100rpm.Obtain the oxygen of logarithmic phase
Change sulphur Thiobacillus bacterium solution.
Thiobacillus thioxidans culture medium includes the following components: (NH of 0.24g/L4)2SO4, the KCl of 0.1g/L, 0.50g/L
K2HPO4, the MgSO of 0.50g/L4·7H2Ca (the NO of O, 0.01g/L3)2, the Na of 5g/L2S2O3, pH 2.0, solvent is water.
Ferrous oxide hook end spirillum and Thiobacillus thioxidans microbial inoculum proportion: by ferrous oxide hook end spirillum and sulfur oxide
The logarithmic phase bacterium solution of Thiobacillus distinguishes 1:0,1:1,1:2,2:3,3:2,2:1,0:1 ratio mixing match by volume, successively
To the thalline quantity of ferrous oxide hook end spirillum and Thiobacillus thioxidans than be respectively 1:0,1:1,1:2,2:3,3:2,2:1,
Microbial inoculum after proportion is inoculated in the mix bacterium agent culture medium of 3000ml by the microbial inoculum of 0:1 by the inoculum concentration of 5% (v/v),
100rpm, 28 DEG C of cultures are spare to logarithmic phase, obtain the fermentation liquid containing composite bacteria agent.
Mix bacterium agent culture medium includes the following components: (NH of 0.10g/L4)2SO4, the KCl of 0.1g/L, 0.50g/L's
K2HPO4, the MgSO of 0.50g/L4·7H2Ca (the NO of O, 0.01g/L3)2, the FeSO of 10g/L4The Na of 7H2O, 1g/L2S2O3,
PH is 1.8, and solvent is water.
Embodiment 1B
The culture of ferrous oxide hook end spirillum:
The deposit number of ferrous oxide hook end spirillum is specially CCTCC AB 206158,206159 and of CCTCC AB
CCTCC AB 206160, three kinds of bacterium thalline quantities etc. are than mixing.
Ferrous oxide hook end spirillum is inoculated in ferrous oxide hook end spiral bacterium culture medium with the bacterium amount that connects of 10% (v/v)
In, 30 DEG C, fermented and cultured in the shaking table of 110rpm.Obtain the ferrous oxide hook end spirillum bacterium solution of logarithmic phase.
Ferrous oxide hook end spiral bacterium culture medium includes the following components: (NH of 0.24g/L4)2SO4, the KC l of 0.1g/L,
The K of 0.50g/L2HPO4, the MgSO of 0.50g/L4·7H2Ca (the NO of O, 0.01g/L3)2, the FeSO of 40g/L4·7H2O, pH 2,
Solvent is water.
The culture of Thiobacillus thioxidans:
Thiobacillus thioxidans is specially CCTCC AB 206195 and CCTCC AB 206196, the ratio such as two kinds of bacterium thalline quantities
Mixing.
Thiobacillus thioxidans is inoculated in Thiobacillus thioxidans culture medium with the bacterium amount that connects of 10% (v/v), 30 DEG C,
Fermented and cultured in the shaking table of 110rpm.Obtain the Thiobacillus thioxidans bacterium solution of logarithmic phase.
Thiobacillus thioxidans culture medium includes the following components: (NH of 0.24g/L4)2SO4, the KCl of 0.1g/L, 0.50g/L
K2HPO4, the MgSO of 0.50g/L4·7H2Ca (the NO of O, 0.01g/L3)2, the Na of 8g/L2S2O3, pH 2.4, solvent is water.
Ferrous oxide hook end spirillum and Thiobacillus thioxidans microbial inoculum proportion: by ferrous oxide hook end spirillum and sulfur oxide
1:0,1:1,1:2,2:3,3:2,2:1,0:1 ratio mixing match successively obtain the logarithmic phase bacterium solution of Thiobacillus by volume respectively
To the thalline quantity of ferrous oxide hook end spirillum and Thiobacillus thioxidans than be respectively 1:0,1:1,1:2,2:3,3:2,2:1,
Microbial inoculum after proportion is inoculated in the mix bacterium agent culture medium of 3000ml by the microbial inoculum of 0:1 by the inoculum concentration of 10% (v/v),
110rpm, 30 DEG C of cultures are spare to logarithmic phase, obtain the fermentation liquid containing composite bacteria agent.
Mix bacterium agent culture medium includes the following components: (NH of 0.10g/L4)2SO4, the KCl of 0.1g/L, 0.50g/L's
K2HPO4, the MgSO of 0.50g/L4·7H2Ca (the NO of O, 0.01g/L3)2, the FeSO of 30g/L4·7H2The Na of O, 5g/L2S2O3, pH
It is 2.2, solvent is water.
Embodiment 1C
The culture of ferrous oxide hook end spirillum:
The deposit number of ferrous oxide hook end spirillum is specially CCTCC AB 206164, CCTCC AB 207036, CCTCC
AB 207037 and CCTCC AB 207038, four kinds of bacterium thalline quantities etc. are than mixing.
Ferrous oxide hook end spirillum is inoculated in ferrous oxide hook end spiral bacterium culture medium with the bacterium amount that connects of 10% (v/v)
In, 32 DEG C, fermented and cultured in the shaking table of 120rpm.Obtain the ferrous oxide hook end spirillum bacterium solution of logarithmic phase.
Ferrous oxide hook end spiral bacterium culture medium includes the following components: (NH of 0.30g/L4)2SO4, the KCl of 1.0g/L,
The K of 5.0g/L2HPO4, the MgSO of 5.0g/L4·7H2Ca (the NO of O, 0.1g/L3)2, the FeSO of 50g/L4·7H2O, pH 2.2,
Solvent is water.
The culture of Thiobacillus thioxidans:
Thiobacillus thioxidans is specially CCTCC AB 206195, CCTCC AB 206196 and CCTCC AB206197, and three
Kind bacterium thalline quantity etc. is than mixing.Thiobacillus thioxidans is inoculated in Thiobacillus thioxidans culture with the bacterium amount that connects of 10% (v/v)
In base, 32 DEG C, fermented and cultured in the shaking table of 120rpm.Obtain the Thiobacillus thioxidans bacterium solution of logarithmic phase.
Thiobacillus thioxidans culture medium includes the following components: (NH of 0.30g/L4)2SO4, the KCl of 1.0g/L, 5.0g/L's
K2HPO4, the MgSO of 5.0g/L4·7H2Ca (the NO of O, 0.1g/L3)2, the Na of 10g/L2S2O3, pH 3.0, solvent is water.
Ferrous oxide hook end spirillum and Thiobacillus thioxidans microbial inoculum proportion: by ferrous oxide hook end spirillum and sulfur oxide
The logarithmic phase bacterium solution of Thiobacillus distinguishes 1:0,1:1,1:2,2:3,3:2,2:1,0:1 ratio mixing match by volume, successively
To the thalline quantity of ferrous oxide hook end spirillum and Thiobacillus thioxidans than be respectively 1:0,1:1,1:2,2:3,3:2,2:1,
Microbial inoculum after proportion is inoculated in the mix bacterium agent culture medium of 3000ml by the microbial inoculum of 0:1 by the inoculum concentration of 10% (v/v),
120rpm, 32 DEG C of cultures are spare to logarithmic phase, obtain the fermentation liquid containing composite bacteria agent.
Mix bacterium agent culture medium includes the following components: (NH of 0.24g/L4)2SO4, the KCl of 1.0g/L, 5.0g/L's
K2HPO4, the MgSO of 5.0g/L4·7H2Ca (the NO of O, 0.1g/L3)2, the FeSO of 30g/L4The Na of 7H2O, 5g/L2S2O3, pH
It is 2.2, solvent is water.
Embodiment 2: composite bacteria agent handles the cultivation exhaust gas effect detection in cattle farm, chicken farm
The cultivation exhaust gas main component H of cattle farm, chicken farm2S and NH3, every cubic metre contains 0.0084~0.0088mg's
H2The NH of S and 2.015~2.025mg3, laboratory simulation cultivates waste gas component, with the draft speed of 100~200ml/min, point
It is not passed through in the fermentation liquid containing composite bacteria agent of the preparation of embodiment 1.In composite bacteria agent, ferrous oxide hook end spirillum and oxidation
The volume ratio of sulphur Thiobacillus is respectively 1:0,1:1,1:2,2:3,3:2,2:1,0:1.After ventilation 2 hours, collects and detect whole
H in tail gas2S and NH3Content.Calculate H2S and NH3Average removal efficiency.Average removal efficiency is as shown in table 1.
Table 1
It was found that, individually the removal efficiency of ferrous oxide hook end spirillum and independent Thiobacillus thioxidans does not reach
To 90%, and individually, ferrous oxide hook end spirillum and individual Thiobacillus thioxidans cannot be used for a long time.Ferrous oxide
Hook end spirillum cannot utilize sulphur source；Thiobacillus thioxidans reduces in environment activity of the pH less than 2.
Interpretation of result obtains, using the microbial inoculum of ferrous oxide hook end spirillum and the compound preparation of Thiobacillus thioxidans, H2S is flat
Equal removal efficiency and NH3Average removal efficiency is up to 92% or more, when the body of ferrous oxide hook end spirillum and Thiobacillus thioxidans
Product, H more best than the composite bacteria agent removal effect prepared for 2:32The S removal efficiency that is averaged reaches 99.5%, NH3Average removal efficiency is reachable
99.4%.
Embodiment 3: the cultivation exhaust gas effect detection of composite bacteria agent processing pig farm
The cultivation exhaust gas main component H of pig farm2S and NH3, every cubic metre of H containing 0.0165~0.0175mg2S with
The NH of 0.5790~0.5800mg3, laboratory simulation cultivates waste gas component, with the draft speed of 100~200ml/min, difference
It is passed through the fermentation liquid that 3000ml contains composite bacteria agent.In composite bacteria agent, ferrous oxide hook end spirillum and Thiobacillus thioxidans body
Product is than being respectively 1:0,1:1,1:2, and 2:3,3:2, the composite bacteria agent of 2:1,0:1,3 parallel.After ventilation 2 hours, detection is different
Cultivation exhaust gas is passed through after different proportion composite bacteria agent H in tail gas2S and NH3Content.Calculate H2S and NH3Average removal efficiency.It is average
Removal efficiency is as shown in table 2.
Table 2
Interpretation of result obtains, using the microbial inoculum of ferrous oxide hook end spirillum and the compound preparation of Thiobacillus thioxidans, H2S is flat
Equal removal efficiency and NH3Average removal efficiency is up to 92% or more, when the body of ferrous oxide hook end spirillum and Thiobacillus thioxidans
Product, H more best than the composite bacteria agent removal effect prepared for 2:32The S removal efficiency that is averaged reaches 99.5%, NH3Average removal efficiency is reachable
98.2%.
Embodiment 4: composite bacteria agent handles sewage treatment plant's exhaust gas effect detection
In sewage treatment plant's exhaust gas, every cubic metre of exhaust gas contains the H of 1.2~9.1mg2The NH of S and 2.1~3.8mg3, real
Room analog culture waste gas component is tested, with the draft speed of 100~200ml/min, 3000ml is each led into and contains composite bacteria agent
Fermentation liquid.In composite bacteria agent, ferrous oxide hook end spirillum and Thiobacillus thioxidans ratio are 1:0,1:1,1:2,2:3,3:2,
The composite bacteria agent of 2:1,0:1,3 parallel.Detection different breeding exhaust gas is passed through after different proportion composite bacteria agent H in tail gas2S and NH3
Content.Calculate H2S and NH3Average removal efficiency.Average removal efficiency is as shown in table 3.
Table 3
Interpretation of result obtains, using the microbial inoculum of ferrous oxide hook end spirillum and the compound preparation of Thiobacillus thioxidans, H2S is flat
Equal removal efficiency and NH3Average removal efficiency is up to 92% or more, when the body of ferrous oxide hook end spirillum and Thiobacillus thioxidans
Product than for the composite bacteria agent removal effect that is prepared when 2:3 it is best, H2The S removal efficiency that is averaged reaches 99.4%, NH3Average removal efficiency can
Up to 95.2%.
Collection of products after 5 composite bacteria agent desulfurization deamination of embodiment
By the logarithmic phase bacterium solution of ferrous oxide hook end spirillum and Thiobacillus thioxidans, 2:3 is mixed by volume in embodiment 1A
It closes the composite bacteria agent being prepared into and absorbs H2S and NH3, when fermented and cultured about 48 is small after, precipitating can be generated, will precipitating with 1~1.5M
10~12h of HCl soaking at room temperature after, be centrifuged 10min through 10000rpm, collect precipitating, be dried under vacuum to constant weight, mixed
Object, i.e. yellow KFe3(SO4)2(OH)6、H3OFe3(SO4)2(OH)6And NH4Fe3(SO4)2(OH)6Solid.
Embodiment 6: autunezite is prepared with composite bacteria agent
It is as follows that embodiment 6A prepares autunezite method:
(1) by composite bacteria agent, (composite bacteria agent is in embodiment 1A by ferrous oxide hook end spirillum and sulfur oxide sulphur bar
The logarithmic phase bacterium solution composite bacteria agent that 2:3 is prepared by mixing by volume of bacterium) 3000ml is inoculated in the inoculum concentration of 10% (v/v)
(culture medium is added with the K of 10g/L to desulfurization deamination composite bacteria agent culture medium2SO4), after 120rpm, 30 DEG C of culture 48h, ferrous oxygen
Rate reaches 90%, has precipitating to generate at this time；
(2) precipitating for generating step (1) is centrifuged 10min through 10000rpm, is collected with after the HCl soaking at room temperature 10h of 1M
Precipitating；
(3) dilute hydrochloric acid of precipitating distilled water or percentage by volume 5% that step (2) are collected is washed, is filtered, filter residue is true
Sky is dry to constant weight, obtains autunezite powder (25.57g) after grinding.
It is as follows that embodiment 6B prepares autunezite method:
(1) by composite bacteria agent, (composite bacteria agent is in embodiment 1B by ferrous oxide hook end spirillum and sulfur oxide sulphur bar
The logarithmic phase bacterium solution composite bacteria agent that 2:3 is prepared by mixing by volume of bacterium) 3000ml is inoculated in the inoculum concentration of 5% (v/v)
(culture medium is added with the K of 10g/L to desulfurization deamination composite bacteria agent culture medium2SO4), after 120rpm, 30 DEG C of culture 48h, ferrous oxygen
Rate reaches 80%, has precipitating to generate at this time；
(2) precipitating (22.39g) for generating step (1) is centrifuged with after the HCl soaking at room temperature 10h of 1M through 10000rpm
10min collects precipitating；
(3) dilute hydrochloric acid that precipitating distilled water or percentage by volume that step (2) are collected are 5% is washed, is filtered, filter residue
It is dried under vacuum to constant weight, obtains autunezite powder (21.92g) after grinding.
It is as follows that embodiment 6C prepares autunezite method:
(1) by composite bacteria agent, (composite bacteria agent is in embodiment 1C by ferrous oxide hook end spirillum and sulfur oxide sulphur bar
The logarithmic phase bacterium solution composite bacteria agent that 2:3 is prepared by mixing by volume of bacterium) 3000ml is inoculated in the inoculum concentration of 10% (v/v)
(culture medium is added with the K of 10g/L to desulfurization deamination composite bacteria agent culture medium2SO4), after 120rpm, 32 DEG C of culture 48h, ferrous oxygen
Rate reaches 90%, has precipitating to generate at this time；
(2) precipitating for generating step (1) is centrifuged 10min through 10000rpm, is received with after the HCl soaking at room temperature 12h of 1.5M
Collection precipitating；
(3) dilute hydrochloric acid of precipitating distilled water or percentage by volume 8% that step (2) are collected is washed, is filtered, filter residue is true
Sky is dry to constant weight, obtains autunezite powder (20.57g) after grinding.
Comparative example:
Comparative example 1: embodiment 1A (in embodiment 1A, pair of ferrous oxide hook end spirillum and Thiobacillus thioxidans
2:3 is mixed number phase bacterium solution by volume) on the basis of, ferrous oxide hook end spirillum is replaced with into leptospirillum ferriphilum
(Leptospirillum ferriphilum) DSM-14647, other are identical as 1A is implemented, using the method in embodiment 2
Detect the cultivation exhaust gas effect in cattle farm, chicken farm.Autunezite is prepared using the method for embodiment 6A.
Comparative example 2: embodiment 1A (in embodiment 1A, pair of ferrous oxide hook end spirillum and Thiobacillus thioxidans
2:3 is mixed number phase bacterium solution by volume) on the basis of, ferrous oxide hook end spirillum is replaced with into ferrous oxide hook end spirillum
(Leptospirillum ferrooxidans)29047, other are identical as 1A is implemented, using the side in embodiment 2
Method detects the cultivation exhaust gas effect in cattle farm, chicken farm.Autunezite is prepared using the method for embodiment 6A.
Comparative example 3: embodiment 1A (in embodiment 1A, pair of ferrous oxide hook end spirillum and Thiobacillus thioxidans
2:3 is mixed number phase bacterium solution by volume) on the basis of, Thiobacillus thioxidans is replaced with into Thiobacillus ferrooxidans
(Acidithiobacillus ferrooxidans BYM) CCTCC2018630, other are identical as 1A is implemented, using implementation
The cultivation exhaust gas effect of method detection cattle farm, chicken farm in example 2.Autunezite is prepared using the method for embodiment 6A.
Comparative example 4: embodiment 1A (in embodiment 1A, pair of ferrous oxide hook end spirillum and Thiobacillus thioxidans
Number phase bacterium solution is 2:3 mixing by volume) on the basis of, Thiobacillus thioxidans is replaced with into Thiobacillus thioxidans
Acidithiobacillus thiooxidans19377TM, other are identical as 1A is implemented, using in embodiment 2
Method detects the cultivation exhaust gas effect in cattle farm, chicken farm.Autunezite is prepared using the method for embodiment 6A.
Bacterial strain in comparative example is deposited in the Culture Collection Center such as DSMZ, CCTCC, ATCC, can pass through commercially available acquisition.
Experimental result is as shown in table 4.
Table 4
The experimental results showed that ferrous oxide hook end spirillum is selected to compound with Thiobacillus thioxidans with H2S removal efficiency height,
NH3The advantages that removal efficiency is high and autunezite yield is high.It is CCTCC AB when ferrous oxide hook end spirillum is selected from deposit number
206158、CCTCC AB 206159、CCTCC AB 206160、CCTCC AB 206161、CCTCC AB 206162、CCTCC
The bacterium of AB 206163, CCTCC AB 206164, CCTCC AB 207036, CCTCC AB 207037, CCTCC AB 207038
Strain one or more of, Thiobacillus thioxidans be selected from deposit number be CCTCC AB 206195, CCTCC AB 206196,
When one or more of the bacterial strain of CCTCC AB 206197, H can be further improved2S removal efficiency height, NH3Removal efficiency height with
And autunezite yield.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of microbial inoculum of simultaneous removing hydrogen sulfide and ammonia, which is characterized in that including ferrous oxide hook end spirillum and oxidation
Sulphur Thiobacillus.
2. a kind of simultaneous removing H according to claim 12S and NH3Microbial inoculum, which is characterized in that the ferrous oxide hook end
It is CCTCC AB 206158, CCTCC AB 206159, CCTCC AB 206160, CCTCC AB that spirillum, which is selected from deposit number,
206161、CCTCC AB 206162、CCTCC AB 206163、CCTCC AB 206164、CCTCC AB 207036、CCTCC
One or more of the bacterial strain of AB 207037, CCTCC AB 207038.
3. a kind of microbial inoculum of simultaneous removing hydrogen sulfide and ammonia according to claim 1, which is characterized in that Thiobacillus thioxidans
Selected from deposit number be CCTCC AB 206195, one of bacterial strain of CCTCC AB 206196, CCTCC AB 206197 or several
Kind.
4. any one of -3 a kind of microbial inoculum of simultaneous removing hydrogen sulfide and ammonia according to claim 1, which is characterized in that oxidation
The thalline quantity ratio of ferrous hook end spirillum and Thiobacillus thioxidans is (35-45): (55-65).
5. application of any one of the claim 1-4 microbial inoculum in desulfurization and/or deamination.
6. any one of the claim 1-4 microbial inoculum is in preparation KFe3(SO4)2(OH)6、H3OFe3(SO4)2(OH)6And/or NH4Fe3
(SO4)2(OH)6In application.
7. a kind of preparation method of any one of claim 1-4 microbial inoculum, which comprises the following steps: will aoxidize
Ferrous hook end spirillum and Thiobacillus thioxidans are cultivated respectively to logarithmic phase, and ferrous oxide hook end spirillum bacterium solution and oxidation are obtained
Sulphur Thiobacillus bacterium solution later mixes the ferrous oxide hook end spirillum bacterium solution and Thiobacillus thioxidans bacterium solution of logarithmic phase, is made
Microbial inoculum.
8. a kind of preparation method of any one of claim 1-4 fermentation liquid of the microbial inoculum, which is characterized in that microbial inoculum to be inoculated into
In culture medium, fermented and cultured obtains the fermentation liquid of microbial inoculum.
9. a kind of using any one of the claim 1-4 microbial inoculum desulfurization and/or the method for deamination, which is characterized in that including with
Lower step:
(1) microbial inoculum is inoculated into culture medium, fermented and cultured, obtains the fermentation liquid containing above-mentioned microbial inoculum；
(2) H will be contained2S and/or NH3Exhaust gas be passed through in the fermentation liquid of microbial inoculum, carry out removing H2S and/or NH3Processing.
10. a kind of method for preparing autunezite using any one of the claim 1-4 microbial inoculum, which is characterized in that including with
Lower step:
(1) microbial inoculum is inoculated into containing K2SO4Desulfurization deamination composite bacteria agent culture medium in, fermented and cultured obtains fermentation liquid and heavy
It forms sediment；
(2) precipitating that step (1) obtains is impregnated with hydrochloric acid solution, is centrifuged, collect precipitating later；
(3) washing of precipitate, the filtering collected step (2), by filter residue and drying, obtain autunezite.
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Citations (2)
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| CN101956071A (en) * | 2010-10-31 | 2011-01-26 | 中南大学 | Biological metallurgy mineral leaching microorganism combined bacterium fluid for copper ore and method for recycling metallic copper |
| CN105542898A (en) * | 2015-12-15 | 2016-05-04 | 辽宁工程技术大学 | Desulphurization method of coal dust via biological oxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101956071A (en) * | 2010-10-31 | 2011-01-26 | 中南大学 | Biological metallurgy mineral leaching microorganism combined bacterium fluid for copper ore and method for recycling metallic copper |
| CN105542898A (en) * | 2015-12-15 | 2016-05-04 | 辽宁工程技术大学 | Desulphurization method of coal dust via biological oxidation |
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