CN108865321A - A kind of coal dust synergistic effect oxidation desulfurizing method that secret bacillus acidophilus participates in - Google Patents

A kind of coal dust synergistic effect oxidation desulfurizing method that secret bacillus acidophilus participates in Download PDF

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CN108865321A
CN108865321A CN201811119631.XA CN201811119631A CN108865321A CN 108865321 A CN108865321 A CN 108865321A CN 201811119631 A CN201811119631 A CN 201811119631A CN 108865321 A CN108865321 A CN 108865321A
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coal dust
bacillus acidophilus
culture medium
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coal
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朱宏飞
朱龙
丁宁
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Liaoning Technical University
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Liaoning Technical University
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L9/00Treating solid fuels to improve their combustion

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Abstract

The invention discloses a kind of coal dust synergistic effect oxidation desulfurizing method that concealed bacillus acidophilus participates in, processing step is:The Spawn incubation of the ore-leaching bacterias such as concealed bacillus acidophilus;The foundation of desulfurization leaching ore body system;Soak mine desulfurization;Coal dust is handled after soaking mine;Coal dust is dry;The sulfur-bearing rate of coal dust measures;The desulfurization results of coal dust are evaluated.Concealed bacillus acidophilus ATCC 33463 is used for the collaboration biological oxidation desulfurization of coal dust by the present invention for the first time, by restoring Fe3+At Fe2+Power is provided for Thiobacillus ferrooxidans and ferrous oxide hook end spirillum, the present invention passes through the bioleaching that the close synergistic effect of three kinds of bacteriums of chemautotrophy and heterotrophism is completed at normal temperatures and pressures, in conjunction with coal dust post-processing approach, sulphur in coal dust is oxidized to sulfate to be dissolved in water and separate with coal dust, the desulfurization degree of treated coal dust is respectively 16.37% and 20.33%, effectively reduces potential sulfur dioxide pollution.

Description

A kind of coal dust synergistic effect oxidation desulfurizing method that secret bacillus acidophilus participates in
Technical field
The invention belongs to microbiology and mineralogical technical field more particularly to a kind of coals that concealed bacillus acidophilus participates in Powder synergistic effect oxidation desulfurizing method.
Background technique
Coal has in the economic growth and industrialization of developing country and lifts as a kind of main energy reserves in world The effect of sufficient weight, since its price is lower, convenient sources, the departments such as thermal power generation and heat treatment are dependent on such energy. Therefore, 90% sulphur is all discharged into air in the form of sulphur dioxide in combustion in coal.Sulfur dioxide is to week Serious pollution is caused in collarette border, and acid rain is exactly this pollution as a result, since acid rain has serious harm to the ecosystem Property, environmental protection administration all over the world all is doing one's utmost to prevent the generation of acid rain.Sulfur content is divided into six from low to high in coal in China Grade is normally contained within the scope of 0.38~5.32%, and with the increase of the coal seam depth of excavation, the sulfur content of coal has Increase trend.Inorganic sulfur in coal mainly exists in the form of the crystallizations such as pyrite and sulfate, organic sulfur mainly with mercaptan, The forms such as thioether and dibenzothiophenes (DBT) are main existence form.The content of sulphur is in the choice of this fuel at extremely pass Important factor.Use is forbidden always or limited to sulphur coal and medium sulphur coal for this reason, low-sulfur coal allow using, and In recent years have sizable market potential.With the continuous exhaustion of domestic and international fuel source, inevitably utilization The high sulphur content of target diversion coal resources.In order to reduce the SO2 emissions of atmosphere, promotes economic sustainable development, compel Desulfurization will be carried out to coal by being essential, and this technology is also referred to as biologic cleanliness coal technology, the potentiality with large-scale commercial applications application.
The sulfur method of coal dust has very much, and biological desulfurization method most has development potentiality.These methods are substantially included in object Within logos, chemical method and biological oxidation process.Physical method mainly removes pyrite, is inhaled using the magnetism of iron-stone, surface Luminosity and surface nature sorted, electrostatic separation and jigging etc., is separated to containing sulfur granules, by magnetic, charge and close The parameters such as degree are separated, it the shortcomings that be organic sulfur removal effect it is poor, for short grained coal dust treatment effect compared with It is weak.Chemical method desulfurization is that the chemical reactions such as oxidation, reduction, pyrolysis occur by chemical reagent such as strong acid, strong oxidizers, sulphur oxygen The element sulphur changed or the abjections such as sulphur displacement are wherein contained.Chemical method is that the sulphur in coal dust is transformed into non-beam from bound state State is tied up, that is, forms liquid or gaseous sulfide or sulfate species, then sulfur-containing compound is extracted, finally Achieve the purpose that desulfurization.This chemical method can be by coal dust 25%~70% organic removal of sulphur.The shortcomings that chemical method It is to generate a large amount of coal dust to dispose waste liquid, using substances such as a large amount of acid and strong oxidizers, the processing method of higher cost, and Still there is potential environmental hazard.
Summary of the invention
Based on the above the deficiencies in the prior art, technical problem solved by the invention is to provide a kind of concealed bacillus acidophilus The coal dust synergistic effect oxidation desulfurizing method of participation enables the sulphur in coal to deviate from using the redox degradation reaction of biology A kind of low power consuming method, desulfurization is more thorough.
In order to solve the above-mentioned technical problem, the present invention is achieved through the following technical solutions:
The present invention provides a kind of coal dust synergistic effect oxidation desulfurizing method that concealed bacillus acidophilus participates in, including following step Suddenly:
S1,9K and 9KG culture medium is prepared;
The Spawn incubation of S2, ore-leaching bacteria:Thiobacillus ferrooxidans and ferrous oxide hook end spirillum use 9K culture medium Culture;Concealed bacillus acidophilus uses the culture of 9KG culture medium, is aseptically inoculated with;
The preparation of S3, ore pulp:The coal dust of 150 mesh is added in the culture medium that 9K and 9KG is mixed and obtains ore pulp;
S4, the microbionation for soaking ore body system:Three kinds of bacterium solutions being separately added into the ore pulp of step S3 in step S2, wherein The volume proportion of three kinds of bacterium solutions is:Concealed bacillus acidophilus:Thiobacillus ferrooxidans:Ferrous oxide hook end spirillum=1:1:1;
S5, leaching mine:Shaking table culture is carried out using ore pulp of the constant temperature air bath shaker incubator to step S4 and soaks mine;
S6, coal powder collection:By the ore pulp of step S5 successively by being collected by centrifugation;
S7, coal dust cleaning:Using the salts substances on heat alkali liquid cleaning coal dust surface;
S8, cleaning solution processing:The cleaning solution of step S7 is collected, and is sufficiently precipitated, measure and adjusts pH to sewage It is discharged after discharge standard;
S9, coal powder natural are dry:The coal powder natural drying of step S7 is no longer mitigated to weight;
The desulfurization degree measurement of S10, coal dust:Using the content of element sulphur in infrared sulphur detector measurement coal dust;
The desulfurization degree calculating of S11, coal dust.
By upper, concealed bacillus acidophilus is to play heterotrophism reduction iron ion (Fe3+) effect, while utilize ferrous oxide sulphur bar The debirs that bacterium and ferrous oxide hook end spirillum generate during soaking mine reduce adverse effect of the organic matter to the two. Three kinds of bacteriums are all acidophilic bacterias in leaching ore body system of the invention, they work in coordination and supplement in metabolism, rise from each other The effect for promoting growth is arrived, so as to sufficiently remove the element sulphur in coal dust.In addition, treatment process of the invention is simpler It is single, it is easily operated, do not need special place and equipment.
Preferably, in step sl, the preparation of 9K culture medium includes:
(NH4) is added in distilled water2SO4, K2HPO4·3H2O, MgSO4·7H2O, Ca (NO3)2, all adjusted after dissolution The FeSO of filtration sterilization is added in pH to 2.0-2.5,121 DEG C of sterilizing 20min after sterilizing4·7H2O, wherein (NH4)2SO4, K2HPO4·3H2O, MgSO4·7H2O, Ca (NO3)2And FeSO4·7H2The concentration of O is respectively 3g/L, 0.5g/L, 0.5g/L, 0.1g/L and 10g/L obtains 9K culture medium;
The preparation of 9KG culture medium includes:
(NH4) is added in distilled water2SO4, K2HPO4, MgSO4·7H2O, KCl, tryptone, glucose, in addition to grape Other than sugar, pH to 3.0-3.5,121 DEG C of sterilizing 20min all are adjusted after dissolution, the glucose of filtration sterilization is added after sterilizing, In (NH4)2SO4, K2HPO4, MgSO4·7H2The concentration of O, KCl, tryptone and glucose is respectively 2.0g/L, 0.5g/L, 0.5g/L, 0.1g/L, 0.1g/L and 1g/L obtain 9KG culture medium.
Further, in step s 2, by three kinds of bacterium solutions after inoculation be put into constant temperature air bath shaker concussion and cultivate case into Row culture, parameter setting temperature are 30~35 DEG C, and revolving speed is 100~150rpm, shaking table 5~7d of shaken cultivation, until logarithmic phase, oxygen Change ferrous Thiobacillus and ferrous oxide hook end spirochaete culture is in brownish red;Concealed bacillus acidophilus's culture solution is in cloudy state.
In step s3, the ratio of the 9K culture medium in the culture medium of 9K and 9KG mixing and 9KG culture medium is 2:1, wherein The dosage of coal dust is 10% (W/V), obtains the ore pulp that concentration is 10%;PH value is adjusted to 3.2-3.8.
In step s 4, total volume of three kinds of bacterium solutions in system after addition is 5% (V/V).
By upper, the ability of the reduction iron ion of concealed bacillus acidophilus and the characteristic of heterotrophism are given full play to, this characteristic is association The key point of same-action, ensured Thiobacillus ferrooxidans and ferrous oxide hook end spirillum not by the murder by poisoning of organic matter, really Thiobacillus ferrooxidans is protected to supply the oxidation kinetics of element sulphur.
In step s 5, the temperature used in mine culture is soaked for 30~35 DEG C, and revolving speed is 100~150rpm, soaks the mine time It is 7~11 days, measures the conductivity, oxidation-reduction potential and pH value of ore pulp every three days using multi-parameter water quality measuring instrument therebetween Situation of change monitors the terminal of redox reaction.
In the step s 7, NaOH powder will be added in the leaching pit coal powder tentatively cleaned, adjusts pH value to 10-12, places 80- 100 DEG C of holding 30min, then being cleaned with 80-100 DEG C of hot water to pH value is 6.5-7.5.
By upper, coal dust is carried out heat alkali liquid to wash with hot water washing purpose to be to remove coal dust surface during soaking mine The sulfate or autunezite substance of attachment, are allowed to fully stay in the liquid phase.
In step s3, the perseverance that the perseverance that the sulfur content of 150 mesh is 1.16% washes grain greatly and sulfur content is 1.18% is washed greatly The coal dust of block is separately added into the culture medium of mixing, and the ore pulp that concentration is 10% is made.
In step s 11, the calculation formula of the desulfurization degree of coal dust is:
RDS=(St-Sn)/St
In formula:RDSFor desulfurization degree (%);StFor the total sulfur content of coal dust raw material;SnFor the sulfur content of coal dust after processing.
By upper, the present invention at least has the advantages that following three:
(1) reasonable ore-leaching bacteria synergistic effect desulfurization system is established
The method of more bacterium synergistic effect processing coal dusts provided by the invention can solve the removing problem of sulfur-bearing ingredient, packet Pyrite, thiophene substance and elemental sulfur etc. are included, these sulfur-bearing ingredients are oxidized to soluble sulfate and are reached into liquid phase To the purpose removed from coal dust.Concealed bacillus acidophilus restores Fe3+As Fe2+, it is Thiobacillus ferrooxidans and ferrous oxide Hook end spirillum provides the power resource for completing biological oxidation.Concealed bacillus acidophilus can also utilize other three kinds of ore-leaching bacterias The organic acid or small organic molecule generated in metabolic process avoids toxic action of the organic matter to chemosynthetic bacteria; Whether Thiobacillus ferrooxidans or ferrous oxide hook end spirillum can provide Fe3+, i.e., bottom needed for concealed bacillus acidophilus Object.Thiobacillus ferrooxidans is mainly to Fe2+Stronger oxidability is kept with reducible sulfur compound;Ferrous oxide hook end spirillum Effect be also iron-oxidizing bacterium, can be Fe2+It is oxidized to Fe3+.Compared to Thiobacillus ferrooxidans, it is to low temperature and ion The better resistance of stress can constantly play oxidability, provide oxidation kinetics for leaching mine process.In short, three kinds of leaching mines are thin Bacterium is worked in coordination in metabolism, and waste is utilized, and is soaked bacterium in ore body system and is in good growth conditions always, to various forms It can be effectively handled with the purpose element of valence state to reach optimal leaching mine purpose.
(2) theory of green economy is pursued throughout
Under the premise of green economy, all economy and scientific and technological activities will be responsible for ecological environment.The ecological value begins It is the measurement standard of all energy utilization patterns eventually.As long as it is economically feasible, and sulfur dioxide (SO2) emissions can be reduced, It is all to be worth attempting.The area of acid rain has been over the 40% of national territorial area at present.Acid rain is to human health, plant, dynamic Object, forest and building etc. all cause negative effect.90% sulfur dioxide (SO2) emissions are all derived from the burning of coal in atmosphere, this Full sulfur removal rate up to 20.33% in invention embodies change energy so reducing the sulfur dioxide (SO2) emissions of respective numbers The objective of source Land use systems.In addition, in the methods of the invention, the sulphur contained in coal dust enters liquid phase in the form of sulfate, give up Liquid is precipitated after collecting, and pH value detection or reconciles etc. after environmental protection treatments qualified discharge again.
(3) easy-to-use method is principle of the invention
Key link of the present invention is leaching mine, so the capital equipment needed is exactly to stir, shake and temperature control device.If place Managing a large amount of coal dusts can be mixed by the way of agitation using the circular capacity pool for having temperature control, rather than limited production Required shaken cultivation mode, can save production cost in this way, to achieve the purpose that sufficiently to soak mine.Other ancillary equipments are exactly The Spawn incubation work that mass production uses.Spawn incubation will use small-sized shaking table and pH meter etc., these equipment are all low values Commodity.Due to this technology have the characteristics that it is simple, easy-operating, staff by brief training can be completed leaching miner Make, does not need special or long-term training.The present invention is exactly small investment on the whole, the project easily implemented.Valence of the invention Value is with investment few as far as possible, exchanges for as much as possible using coal, gives full play to the energy value of coal.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention, And it can be implemented in accordance with the contents of the specification, and in order to allow above and other objects, features and advantages of the invention can It is clearer and more comprehensible, below in conjunction with preferred embodiment, and cooperates attached drawing, detailed description are as follows.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, the attached drawing to embodiment is simply situated between below It continues.
Fig. 1 is the technique flow graph for the coal dust synergistic effect oxidation desulfurizing method that concealed bacillus acidophilus of the invention participates in.
Specific embodiment
The embodiment of the invention will now be described in detail with reference to the accompanying drawings, and as part of this specification passes through Embodiment illustrates the principle of the present invention, and other aspects of the present invention, feature and its advantage will become by the detailed description It is very clear.In the attached drawing of institute's reference, the same or similar component is indicated using identical drawing reference numeral in different figures.
The technical issues of for coal dust biological desulphurization, the present invention provides a kind of coal dust collaborations that concealed bacillus acidophilus participates in Oxidation sulfur method, using by concealed bacillus acidophilus ATCC 33463, Thiobacillus ferrooxidans and ferrous oxide hook end spiral shell It revolves three kinds of bacteriums of bacterium and forms bioleaching system, the desulfurization degree of coal dust can be improved to 16.37~20.33%.
Specifically, as shown in Figure 1, the coal dust synergistic effect oxidation desulfurizing method that concealed bacillus acidophilus of the invention participates in is pressed It is carried out according to following processing step:
(1) 9K and 9KG culture medium is prepared:(NH4) is added in distilled water2SO4, K2HPO4·3H2O, MgSO4·7H2O, Ca(NO3)2, pH to 2.0-2.5,121 DEG C of sterilizing 20min all are adjusted after dissolution, the FeSO of filtration sterilization is added after sterilizing4· 7H2O, wherein (NH4)2SO4, K2HPO4·3H2O, MgSO4·7H2O, Ca (NO3)2And FeSO4·7H2The concentration of O is respectively 3g/ L, 0.5g/L, 0.5g/L, 0.1g/L and 10g/L obtain 9K culture medium;
(NH4) is added in distilled water2SO4, K2HPO4, MgSO4·7H2O, KCl, tryptone, glucose, in addition to grape Other than sugar, pH to 3.0-3.5,121 DEG C of sterilizing 20min all are adjusted after dissolution, the glucose of filtration sterilization is added after sterilizing, In (NH4)2SO4, K2HPO4, MgSO4·7H2The concentration of O, KCl, tryptone and glucose is respectively 2.0g/L, 0.5g/L, 0.5g/L, 0.1g/L, 0.1g/L and 1g/L obtain 9K- glucose, i.e. 9KG culture medium.
(2) Spawn incubation of ore-leaching bacteria:Thiobacillus ferrooxidans and ferrous oxide hook end spirillum use 9K culture medium Culture;Concealed bacillus acidophilus uses the culture of 9KG culture medium, is inoculated under aseptic condition;Three kinds of bacterium solutions after inoculation are put into constant temperature It is cultivated in gas bath shaking table concussion and cultivate case, parameter setting temperature is 30~35 DEG C, and revolving speed is 100~150rpm, shaking table vibration 5~7d of culture is swung, until logarithmic phase, Thiobacillus ferrooxidans and ferrous oxide hook end spirochaete culture are in brownish red;It is concealed thermophilic Acidfast bacilli culture solution is substantially in cloudy state.
(3) preparation of ore pulp:The coal dust of 150 mesh is added in the culture medium that 9K and 9KG is mixed, the ratio of 9K and 9KG are 2:1, wherein the dosage of coal dust is 10% (W/V), obtains the ore pulp that concentration is 10%;PH value is adjusted to 3.2-3.8.
(4) microbionation of ore body system is soaked:Three kinds of bacterium solutions are separately added into the ore pulp of step (3), wherein three kinds of bacterium solutions Volume proportion be:Concealed bacillus acidophilus ATCC 33463:Thiobacillus ferrooxidans:Ferrous oxide hook end spirillum=1:1:1, And total volume of three kinds of bacterium solutions in system is 5% (V/V) after being added;This step is it is significant to note that concealed bacillus acidophilus The addition time of ATCC 33463 is to soak 24 hours after mine starts.Its effect is to play heterotrophism reduction iron ion (Fe3+) Effect, while the debirs generated during soaking mine using Thiobacillus ferrooxidans and ferrous oxide hook end spirillum, are subtracted Few adverse effect of the organic matter to the two.The ability of the reduction iron ion of concealed bacillus acidophilus and the characteristic of heterotrophism are given full play to, This characteristic is the key point of synergistic effect, has ensured Thiobacillus ferrooxidans and ferrous oxide hook end spirillum not by organic The murder by poisoning of object, it is ensured that Thiobacillus ferrooxidans supplies the oxidation kinetics of element sulphur.
(5) mine is soaked:Shaking table culture is carried out using ore pulp of the constant temperature air bath shaker incubator to step (4) and soaks mine, temperature is 30~35 DEG C, revolving speed is 100~150rpm, and the leaching mine time is 7~11 days, therebetween every three days using multi-parameter water quality measuring instrument Conductivity, oxidation-reduction potential and the pH value situation of change for measuring ore pulp, monitor the terminal of redox reaction.
(6) coal powder collection:By the ore pulp of step (5) successively by being collected by centrifugation.
(7) coal dust cleans:Heat alkali liquid cleans the salts substances such as the autunezite on coal dust surface, needs the leaching that will tentatively clean NaOH powder is added in pit coal powder, adjusts pH value to 10-12, places 80-100 DEG C of holding 30min, then use 80-100 DEG C of heat It is 6.5-7.5 that water, which is cleaned to pH value,.The present invention carries out heat alkali liquid washing and heat in the leaching mine last handling process of coal dust, by coal dust The purpose of water washing is to be allowed to fill to remove the coal dust sulfate that surface is adhered to during soaking mine or autunezite substance It stays in the liquid phase with dividing.
(8) cleaning solution is handled:Cleaning solution is collected, is sufficiently precipitated, is measured and carried out after adjusting pH to sewage drainage standard Discharge.Lye and acid solution waste water in the above coal dust treatment process focus on after mutually slowly neutralizing with other waste liquids, meet It is discharged again after discharge standard, strictly avoids secondary pollution.
(9) coal powder natural is dry:The coal powder natural drying of step (7) is no longer mitigated to weight.
(10) the desulfurization degree measurement of coal dust:Using the content of element sulphur in infrared sulphur detector measurement coal dust.
(11) desulfurization degree of coal dust calculates:Desulfurization degree measurement is carried out to synergistic effect treated coal dust, desulfurization degree Calculation formula is:RDS=(St-Sn)/St, in formula:RDSFor desulfurization degree (%);StFor the total sulfur content of coal dust raw material;SnFor processing The sulfur content of coal dust afterwards.
Last handling process of the present invention in step (7) is fairly simple, easily operated, does not need special place and equipment.
The invention belongs to biotechnologys in the application of environment protection field, i.e., slough the member of the sulphur in coal dust with the method for biological oxidation Element.The present invention has concealed bacillus acidophilus (Acidiphilium cryptum, letter in the chemosynthetic autotroph bacterium that leaching mine process uses Claim A.cr), Thiobacillus ferrooxidans (Thiobacillus ferrooxidans, abbreviation T.f) and ferrous oxide hook end spirillum (Leptospirillum ferrooxidans, abbreviation L.f).Wherein concealed bacillus acidophilus (A.cr) is that chemautotrophy is facultative different Bacteria.
Biological desulphurization is a kind of form of coal dust desulfurization before combustion, also referred to as biocatalytic desulfurization, abbreviation BDS method, mainly Through microorganism under conditions of extremely mild, using the redox degradation reaction of biology, make coal or other fossil fuels In sulphur be able to a kind of low power consuming method deviate from.Thiobacillus ferrooxidans has the characteristics that acidophilus, is a kind of chemoautotrophic bacteria, Energy is obtained by ferrous ion, oxidation element sulphur and reducible sulfur compound etc..Oxidation Leaching or de- for metallic ore The processes such as sulphur are largely effective.The oxidation that the elementary sulfur contained in the substances such as the pyrite in coal dust passes through Thiobacillus ferrooxidans Afterwards, by electron transmission, it is finally oxidized to iron ion and sulfuric acid, be dissolved in water and enters liquid phase and is detached from coal, this Kind desulfurization method ratio is more thoroughly.Sulphur in organic phase is also oxidized to sulfuric acid.Under the action of Thiobacillus ferrooxidans, in coal not By being that inorganic sulfur or organic sulfur can be removed by following reactive modes:
4FeS2+15O2+2H2O→2H2SO4+2Fe2(SO4)3
FeS2+14Fe3++8H2O→15Fe2++2S04 2-+16H+
FeS2+2Fe3+→3Fe3++2S
S0+6Fe3++4H2O=6Fe2++S04 2+8H+
2Fe2++1/2O2+2H+→2Fe3++H2O
S0+3/2O2+H2O→H2SO4
Ferrous oxide hook end spirillum is iron-oxidizing bacterium, can be Fe2+It is oxidized to Fe3+, to low temperature and ionic stress It is different to play the time of oxidation from Thiobacillus ferrooxidans, therefore can supplement Thiobacillus ferrooxidans for better resistance Oxidability provides oxidation kinetics for leaching mine process.Whether Thiobacillus ferrooxidans or ferrous oxide hook end spirillum be all Fe can be provided3+, i.e., substrate needed for concealed bacillus acidophilus.Concealed bacillus acidophilus can provide better environment for leaching mine, Fe3 +It is reduced to Fe2+Energy is provided for Thiobacillus ferrooxidans and ferrous oxide hook end spirillum, power resources are provided;It eliminates simultaneously Passivating film caused by iron-containing densification calcified layer etc., increases the area of reaction.
Advantage of the present invention using more bacteriums collaboration biological oxidation, concealed bacillus acidophilus adding for 24 hours after leaching mine starts It is related with its biological effect to enter opportunity.Because concealed bacillus acidophilus is facultative heterotrophic bacteria, it can use ferrous oxide sulphur bar Organic metabolic waste that bacterium and ferrous oxide hook end spirillum generate during the growth process, reduces the murder by poisoning to the above two as best one can Effect, promotes them constantly to play oxidation.The concealed optimal pH value of bacillus acidophilus is 3.2, it adds after leaching mine starts Entering precisely pH value is 3.0 or so, is mutually beneficial in growth conditions.Three kinds of bacteriums are all acidophilic bacterias in this leaching ore body system, They work in coordination and supplement in metabolism, play the role of promoting growth from each other, so as to sufficiently remove coal dust In element sulphur.
Desulfurization method of the invention, which also compares, is suitble to the coal consumers of small-sized dosage to carry out desulfurization before combustion.With other desulfurization Method compares, and of the invention is not limited by place, can handle organic sulfur and inorganic sulfur simultaneously, and removal rate is higher, and required sets Standby simple, cost is also relatively low, and only consumes less energy, and other sulfur methods can not replace.The present invention provides Method it is equally applicable for petroleum sweetening.
Based on the above method, the perseverance of 150 mesh is washed greatly grain (HDXL-1, sulfur content by the embodiment 1 that the present invention uses 1.16%) to be added in mixed culture medium (leaching mine mixed liquor), the ore pulp that concentration is 10%, sample weighing 15g is made.
The perseverance of 150 mesh is washed greatly the addition of block (HDXK-2, sulfur content 1.18%) coal dust and mixed by the embodiment 2 that the present invention uses In the culture medium (leaching mine mixed liquor) of conjunction, the ore pulp that concentration is 10%, sample weighing 15g is made.The embodiment of the present invention uses 2 parts of coal dusts from Liaoning Province Fuxin Mining Group Heng great coal industry Co., Ltd acquire.
Sulfur content is as shown in table 1 before and after the leaching mine of embodiment 1 and embodiment 2:
Table 1:Sulfur-bearing scale before and after two embodiment leaching mines
Application has been obtained in coal dust microorganism synergistic oxidation desulfurization technology of the invention, in metal pollutant processing Effect is had been achieved for, changes that strain used in previous leaching mine process is single, bacterium acts synergistically the efficiency of desulfidation The deleterious situations such as low, leaching mine effect is poor, and ore immersion bacterial culture stress anti-to harmful metal ion is indifferent.The present invention is by concealed acidophilus Bacillus ATCC 33463 is used for the collaboration biological oxidation desulfurization of coal dust for the first time, by restoring Fe3+At Fe2+, it is ferrous oxide sulphur bar Bacterium and ferrous oxide hook end spirillum provide power.The processing method of coal dust is mainly the method for using shaking table bioleaching, is made Element sulphur in coal dust is oxidized to sulfate species and enters liquid phase, the followed by rear place such as heat alkali liquid washing and hot water washing Salts substances of the reason process to remove coal dust surface, so that the method that the content of the full sulphur in coal dust reduces.The present invention is normal The bioleaching that close synergistic effect under normal temperature and pressure by three kinds of bacteriums of chemautotrophy and heterotrophism is completed, after coal dust Sulphur in coal dust is oxidized to sulfate and is dissolved in water and separates with coal dust by reason method, and the desulfurization degree of treated coal dust is respectively 16.37% and 20.33%, effectively reduce potential sulfur dioxide pollution.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.

Claims (9)

  1. The oxidation desulfurizing method 1. a kind of coal dust that secret bacillus acidophilus participates in acts synergistically, which is characterized in that include the following steps:
    S1,9K and 9KG culture medium is prepared;
    The Spawn incubation of S2, ore-leaching bacteria:Thiobacillus ferrooxidans and ferrous oxide hook end spirillum use the culture of 9K culture medium; Concealed bacillus acidophilus uses the culture of 9KG culture medium, is aseptically inoculated with;
    The preparation of S3, ore pulp:The coal dust of 150 mesh is added in the culture medium that 9K and 9KG is mixed and obtains ore pulp;
    S4, the microbionation for soaking ore body system:Three kinds of bacterium solutions being separately added into the ore pulp of step S3 in step S2, wherein three kinds The volume proportion of bacterium solution is:Concealed bacillus acidophilus:Thiobacillus ferrooxidans:Ferrous oxide hook end spirillum=1:1:1;
    S5, leaching mine:Shaking table culture is carried out using ore pulp of the constant temperature air bath shaker incubator to step S4 and soaks mine;
    S6, coal powder collection:By the ore pulp of step S5 successively by being collected by centrifugation;
    S7, coal dust cleaning:Using the salts substances on heat alkali liquid cleaning coal dust surface;
    S8, cleaning solution processing:The cleaning solution of step S7 is collected, and is sufficiently precipitated, measure and adjusts pH to sewage discharge It is discharged after standard;
    S9, coal powder natural are dry:The coal powder natural drying of step S7 is no longer mitigated to weight;
    The desulfurization degree measurement of S10, coal dust:Using the content of element sulphur in infrared sulphur detector measurement coal dust;
    The desulfurization degree calculating of S11, coal dust.
  2. The oxidation desulfurizing method 2. coal dust that secret bacillus acidophilus as described in claim 1 participates in acts synergistically, which is characterized in that In step sl, the preparation of 9K culture medium includes:
    (NH4) is added in distilled water2SO4, K2HPO4·3H2O, MgSO4·7H2O, Ca (NO3)2, all dissolution after adjust pH to The FeSO of filtration sterilization is added in 2.0-2.5,121 DEG C of sterilizing 20min after sterilizing4·7H2O, wherein (NH4)2SO4, K2HPO4· 3H2O, MgSO4·7H2O, Ca (NO3)2And FeSO4·7H2The concentration of O is respectively 3g/L, 0.5g/L, 0.5g/L, 0.1g/L and 10g/L obtains 9K culture medium;
    The preparation of 9KG culture medium includes:
    (NH4) is added in distilled water2SO4, K2HPO4, MgSO4·7H2O, KCl, tryptone, glucose, in addition to glucose with Outside, pH to 3.0-3.5,121 DEG C of sterilizing 20min all are adjusted after dissolution, the glucose of filtration sterilization is added after sterilizing, wherein (NH4)2SO4, K2HPO4, MgSO4·7H2The concentration of O, KCl, tryptone and glucose is respectively 2.0g/L, 0.5g/L, 0.5g/L, 0.1g/L, 0.1g/L and 1g/L obtain 9KG culture medium.
  3. The oxidation desulfurizing method 3. coal dust that secret bacillus acidophilus as described in claim 1 participates in acts synergistically, which is characterized in that In step s 2, three kinds of bacterium solutions after inoculation are put into constant temperature air bath shaker concussion and cultivate case and are cultivated, parameter setting temperature Degree is 30~35 DEG C, and revolving speed is 100~150rpm, shaking table 5~7d of shaken cultivation, until logarithmic phase, Thiobacillus ferrooxidans and oxygen Changing ferrous hook end spirochaete culture is in brownish red;Concealed bacillus acidophilus's culture solution is in cloudy state.
  4. The oxidation desulfurizing method 4. coal dust that secret bacillus acidophilus as described in claim 1 participates in acts synergistically, which is characterized in that In step s3, the ratio of the 9K culture medium in the culture medium of 9K and 9KG mixing and 9KG culture medium is 2:1, the wherein use of coal dust Amount is 10% (W/V), obtains the ore pulp that concentration is 10%;PH value is adjusted to 3.2-3.8.
  5. The oxidation desulfurizing method 5. coal dust that secret bacillus acidophilus as described in claim 1 participates in acts synergistically, which is characterized in that In step s 4, total volume of three kinds of bacterium solutions in system after addition is 5% (V/V).
  6. The oxidation desulfurizing method 6. coal dust that secret bacillus acidophilus as described in claim 1 participates in acts synergistically, which is characterized in that In step s 5, the temperature used in mine culture is soaked for 30~35 DEG C, and revolving speed is 100~150rpm, and the leaching mine time is 7~11 It, measures conductivity, oxidation-reduction potential and pH value the variation feelings of ore pulp every three days using multi-parameter water quality measuring instrument therebetween Condition monitors the terminal of redox reaction.
  7. The oxidation desulfurizing method 7. coal dust that secret bacillus acidophilus as described in claim 1 participates in acts synergistically, which is characterized in that In the step s 7, NaOH powder will be added in the leaching pit coal powder tentatively cleaned, adjusts pH value to 10-12, places 80-100 DEG C of guarantor 30min is held, then being cleaned with 80-100 DEG C of hot water to pH value is 6.5-7.5.
  8. The oxidation desulfurizing method 8. coal dust that secret bacillus acidophilus as claimed in claim 4 participates in acts synergistically, which is characterized in that In step s3, the perseverance that the perseverance that the sulfur content of 150 mesh is 1.16% washes grain greatly and sulfur content is 1.18% is washed greatly to the coal dust of block It is separately added into the culture medium of mixing, the ore pulp that concentration is 10% is made.
  9. The oxidation desulfurizing method 9. coal dust that secret bacillus acidophilus as described in claim 1 participates in acts synergistically, which is characterized in that In step s 11, the calculation formula of the desulfurization degree of coal dust is:
    RDS=(St-Sn)/St
    In formula:RDSFor desulfurization degree (%);StFor the total sulfur content of coal dust raw material;SnFor the sulfur content of coal dust after processing.
CN201811119631.XA 2018-09-25 2018-09-25 A kind of coal dust synergistic effect oxidation desulfurizing method that secret bacillus acidophilus participates in Pending CN108865321A (en)

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