CN106554837B - A kind of method of iron containing compounds and Acidithiobacillus caldus combined removal hydrogen sulfide in methane - Google Patents
A kind of method of iron containing compounds and Acidithiobacillus caldus combined removal hydrogen sulfide in methane Download PDFInfo
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- CN106554837B CN106554837B CN201611010793.0A CN201611010793A CN106554837B CN 106554837 B CN106554837 B CN 106554837B CN 201611010793 A CN201611010793 A CN 201611010793A CN 106554837 B CN106554837 B CN 106554837B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/05—Biogas
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention discloses a kind of methods of iron containing compounds and Acidithiobacillus caldus combined removal hydrogen sulfide in methane, include the following steps: 1) iron containing compounds desulfurization: iron containing compounds are added in the reactor for producing biogas with charging, carries out iron containing compounds desulfurization while marsh gas raw materials fermentation；2) biological desulphurization: the biogas after step 1) iron containing compounds desulfurization is passed into the fermentation liquid of Acidithiobacillus caldus, is collected after detection hydrogen sulfide in methane content is up to standard.Removal efficiency is high, reduces the expense and workload of subsequent desulfurization.After joint removing, hydrogen sulfide in methane content is lower than 5ppm, is more preferably lower than 1ppm, substantially completely removes.
Description
Technical field
The invention belongs to bioenergy technical fields, and in particular to a kind of iron containing compounds and Acidithiobacillus caldus joint
The method for removing hydrogen sulfide in methane.
Background technique
With rapid development of economy, demand for energy increasingly rises all over the world.In energy resource structure, with petroleum, coal
Fossil energy based on charcoal etc., can not be again if the mankind excessively rely on these traditional fossil energies still in occupation of the principal status of public economy
Natural disposition will cause energy crisis.Biogas gradually attracts people's attention as a kind of emerging green energy resource.Biogas is a kind of
Mixed gas generally contains CH4For 60% ~ 70%, CO2It is 30% ~ 40%, a small amount of H2S, steam, NH3Deng.Wherein hydrogen sulfide is to the person
Safety, environment and equipment have biggish harm.For personal safety, hydrogen sulfide has stronger stimulation to mucous membrane, is
Strong neurotoxic substance.For environment, hydrogen sulfide has pollution to water body and air, and the sulfur dioxide for generation of burning causes
The generation of acid rain.For equipment, there is corrosion harmfulness in oil extraction, deposit transport and process, seriously will cause weight
Big safety accident.Biogas purposes is different, to H2The requirement of S content is also different, respective country and professional standard regulation: if utilizing natural pond
Gas generates electricity, then H2The concentration of S need to be less than or equal to 200 ~ 300mg/m3；If biogas as vehicle fuel or is incorporated to gas ductwork,
H2The concentration of S need to be less than or equal to 15mg/m3.H in biogas2The mass concentration of S is generally 1 ~ 12g/m3, considerably beyond in standard
Regulation, if the H contained without pretreatment, in biogas2S can corrode metallic conduit, instrument and meter etc..Therefore, biogas is in synthesis
H must be carried out before2S removing.
Either domestic or external, hydrogen sulfide stripping method has much, can simply be divided into wet desulphurization, dry method
Desulfurization and biological desulphurization.Wet desulphurization is to be reacted with hydrogen sulfide by the specific solvent such as sodium hydroxide, ammonium hydroxide to remove vulcanization
A kind of method of hydrogen reaches recycling for solvent to the effect of solvent by oxygen.Due to the flow velocity and flow of sodium hydroxide
Influence, hydrogen sulfide can not be dissolved completely in wherein, and thiosulfate can be generated in course of dissolution, these are all by shadow
Desulfurization effect is rung, and there are also invest the problems such as more, operational management is complicated, desulphurization cost is high and absorbing liquid needs to change.Dry method is de-
Sulphur is a kind of using oxygen, using iron oxide as oxidant by Oxidation of Hydrogen Sulfide as a kind of desulfurization side of elemental sulfur or sulfide
Formula.Elemental sulfur plays the role of a catalysis in absorption process.But desulfurization by dry method has, and installation area is big, operation
Discontinuously, desulfurizing agent is not easy to regenerate, is not easy the problems such as replacement is low with desulfuration efficiency.Biological desulfurizing technology is to pass through microbial metabolism
Approach is by H2S is converted into a kind of removing sulfuldioxide of sulfate or elemental sulfur.But the stability of its desulfurization is easy by environment temperature
The influence of degree.
Acidithiobacillus caldus (Acidithiobacillus caldus) it is that thiobacillus ferrooxidans belong to
(Acidithiobacillus) in only appropriate Thermophilic Bacteria, it is a kind of Gram-negative bacteria of chemautotrophy that acidophilus is aerobic,
Using sulphur or the sulfide of reproducibility as energy source, with the CO in air2For carbon source, and the inorganic nutrient substances such as absorbed nitrogen, phosphorus
Somatic cells are synthesized, it generally can be by sulphur powder, HS-And H2S is oxidized to H2SO4.Li Yaxin etc. passes through aerobic colorless sulfur bacteria biology
Membrane reactor, has carried out the experiment that sulfide is converted to elemental sulfur, and the removal rate of hydrogen sulfide is up to 87%.
Fe in iron containing compounds desulphurization reaction2+It is the important component of hydrogenase etc. in sulfate reducing bacteria body, while also can
SO is restored with it4 2-The S generated in the process2-Form the minimum FeS precipitating of solubility product.Due to Fe2+Addition, promote it is various
The synthesis of enzyme, the sulfide content reduction eventually led in system even are eliminated.This aspect may be because of Fe3+It can convert
For Fe2+, i.e. Fe3+With S2-Redox reaction occurs and generates Fe2+；Another aspect cell interior Fe2+Activity as enzyme
Based component is also that the effect for realizing place enzyme transmitting electronics is mutually converted by itself valence state.
Summary of the invention
The object of the present invention is to provide a kind of iron containing compounds and Acidithiobacillus caldus combined removal hydrogen sulfide in methane
Method, have easy to operate, process flow is simple, improves utilization of resources value, saves money, improves desulfuration efficiency etc. and is excellent
Point can with stability and high efficiency remove the hydrogen sulfide in biogas, it will help improve biogas utilization level, it is difficult to break through biogas desulfurization
Topic.
To achieve the goals above, the technical scheme adopted by the invention is that:
A kind of method of iron containing compounds and Acidithiobacillus caldus combined removal hydrogen sulfide in methane, including walk as follows
It is rapid:
1) iron containing compounds desulfurization: iron containing compounds are added in the reactor for producing biogas with charging, in marsh gas raw materials
Iron containing compounds desulfurization is carried out while fermentation；
2) biogas after step 1) iron containing compounds desulfurization biological desulphurization: is passed into the fermentation liquid of Acidithiobacillus caldus
In, it is collected after detection hydrogen sulfide in methane content is up to standard.
Iron containing compounds described in step 1) are the mixed of one or more of frerrous chloride, iron chloride or iron hydroxide
It closes.It is preferred that FeCl2: FeCl3: Fe(OH)3=3:1:1。
Concentration of the iron containing compounds described in step 1) in biogas fermentation reactor is 2mM ~ 32mM.It is preferred that iron content chemical combination
The concentration of object is 32mM.
The marsh gas raw materials are at least one of organic wastewater, feces of livestock and poultry, house refuse or stalk etc..In biogas
Original concentration of hydrogen sulfide is 1000ppm ~ 3000ppm.
The Acidithiobacillus caldus is the bacterium that the bacterium numbering of Chinese microorganism strain collection preservation is 1.7296
Strain.
Viable count is 2.0 × 10 in the fermentation liquid of Acidithiobacillus caldus described in step 26A/mL ~ 10.0 × 106
A/mL.
It is 170 r/min that the condition of culture of Acidithiobacillus caldus described in step 2, which is revolving speed, 40 ~ 45 DEG C of temperature.
The culture medium of Acidithiobacillus caldus described in step 2 is 9K culture medium, formula are as follows: A: 3.0 g of ammonium sulfate, chlorine
Change 0.1 g of potassium, 0.5 g of dipotassium hydrogen phosphate, 0.5 g of epsom salt, calcium nitrate 0.01 g, distilled water 1L, with dilute sulfuric acid by pH
2.5 are adjusted to, high pressure sterilization 20min.B: ferrous sulfate 3 ~ 4%, distilled water 10mL cross film degerming.B is added to A culture before inoculation
In base.
The Acidithiobacillus caldus is the bacterium that the bacterium numbering of Chinese microorganism strain collection preservation is 1.7296
Strain, Acidithiobacillus caldus (Acidithiobacillus caldus) it is the extreme acidophilic thiobacillus of a kind of obligate autotrophy, extensively
It is general to be distributed in Sulphide Ore, acid mine water and soil, in the in terms of hair of bacterial metallurgy, the desulfurization of coal and sulfur-containing waste water
Important function is waved, while also being occupied an important position in the sulfur cycle of nature.Dopson and Lindtrom has researched and analysed happiness
The metabolin of warm thiobacillus ferrooxidans has the function of surfactant, and element sulphur is enable sufficiently to be dissolved.Like warm acidophilus sulphur bar
Bacterium oxidability is very strong, and cell, which increases 1g, can generate the elemental sulfur of 20g or more.Biogas after the desulfurization of step 1) original position is continuous
Be passed into the fermentation liquid of Acidithiobacillus caldus, according to the dosage for being passed through rate adaptation fermentation liquid of biogas, with collection
On the basis of hydrogen sulfide in methane content meets required target, adjusted according to treating capacity target.
The cultural method of the bacterial strain are as follows: Acidithiobacillus caldus bacterial strain is subjected to renewal cultivation, is drawn with aseptic straw
The 9K culture medium of 0.3 ~ 0.5mL is instilled in ampoule, is gently shaken, and makes to be lyophilized thallus dissolution in suspension, it is outstanding to draw whole bacterium
Liquid moves in the 9K culture medium of 5mL, sets 170 r/min of mixing speed, 40 ~ 45 DEG C of 48 ~ 72h of culture of temperature, since strain passes through
After freeze-drying saves, period of delay is longer, and the Acidithiobacillus caldus culture solution of generation renewal cultivation is pressed to 3% ~ 5% inoculum concentration
It is inoculated into 5mL fluid nutrient medium, same condition of culture carries out squamous subculture twice in succession, and the happiness temperature of renewal cultivation is thermophilic
Sour Thiobacillus culture solution is inoculated into 80mL fluid nutrient medium by 3% ~ 5% inoculum concentration, and same condition of culture will like warm acidophilus
Thiobacillus is cultivated to logarithmic phase mid-term (4 ~ 5d).
Biogas is passed into the fermentation liquid of Acidithiobacillus caldus and carries out desulfurization, sweetening process control mixing speed is
170 r/min, 40 ~ 45 DEG C of temperature.
The iron containing compounds use solid or liquid.
The good effect that the present invention has is: since the present invention is combined using iron containing compounds and Acidithiobacillus caldus
Sulfur removal technology removes the hydrogen sulfide in biogas, and iron containing compounds are directly added into marsh gas reactor with charging and carry out desulfurization for the first time,
Then the biogas of generation is entered in the B device equipped with 9K culture medium and 3% ~ 5% Acidithiobacillus caldus inoculum concentration, to realize
On-line desulphurization and biological desulphurization carry out combined removal hydrogen sulfide in methane, to significantly reduce hydrogen sulfide in in-situ biogas
Amount removes the hydrogen sulfide harmful to environment and equipment, and removal efficiency is high, reduces the expense and workload of subsequent desulfurization.
After joint removing, hydrogen sulfide in methane content is lower than 5ppm, is more preferably lower than 1ppm, substantially completely removes.
Detailed description of the invention
Fig. 1 is reaction unit figure.
Specific embodiment
With reference to the accompanying drawing, specific embodiments of the present invention is described in detail.
Acidithiobacillus caldus is by Chinese microorganism strain collection preservation, bacterium numbering 1.7296.Implement below
Raw material of the organic wastewater as biogas production is used in example.
Embodiment 1
The present embodiment provides a kind of FeCl that various concentration is added2On-line desulphurization and Acidithiobacillus caldus strain is added
The experiment of biological desulphurization progress combined removal hydrogen sulfide in methane.
Acidithiobacillus caldus bacterial strain is carried out renewal cultivation by step 1, is trained with the 9K that aseptic straw draws 0.3 ~ 0.5mL
Base is supported, instills in ampoule, gently shakes, makes to be lyophilized thallus dissolution in suspension, draws whole bacteria suspensions, move to the 9K training of 5mL
It supports in base, sets 170 r/min of mixing speed, 40 ~ 45 DEG C of 48 ~ 72h of culture of temperature, since strain is after freeze-drying saves,
Period of delay is longer, and the Acidithiobacillus caldus culture solution of generation renewal cultivation is inoculated into the training of 5mL liquid by 3% ~ 5% inoculum concentration
It supports in base, same condition of culture carries out squamous subculture twice in succession, by the Acidithiobacillus caldus culture solution of renewal cultivation
It is inoculated into 80mL fluid nutrient medium by 3% ~ 5% inoculum concentration, same condition of culture is by Acidithiobacillus caldus culture to right
The interim phase (4 ~ 5d) of number.The culture medium prescription of Acidithiobacillus caldus are as follows: A: 3.0 g of ammonium sulfate, 0.1 g of potassium chloride, phosphoric acid hydrogen
PH is adjusted to 2.5 with dilute sulfuric acid, high pressure sterilization by 0.5 g of dipotassium, 0.5 g of epsom salt, calcium nitrate 0.01 g, distilled water 1L
20min.B: ferrous sulfate 3 ~ 4%, distilled water 10mL cross film degerming.B is added in A culture medium before inoculation.
It is 3.78 that step 2, which is 29,000mg/L, pH using alcohol waste water COD (COD), and total nitrogen is
74.84mg/L, general volatile fatty acid (VFAs) are 21.45 mM, activated sludge volatile suspended solid VSS(36.49 g
/ L) fermentation liquid, the fermentation liquid as generate biogas raw material；
Step 3, takes 7 groups of desulfurizers, number A0 to A6, and the resulting fermentation of 80mL step 2 is added in each desulfurization A device
Liquid；
Step 4, takes 7 groups of combined desulfurization devices, number B0 to B6, and 80mL step 2 institute is added in each combined desulfurization A device
The 9K culture medium of 80mL, the warm acidophilus of the resulting happiness of 3% ~ 5% step 1 of inoculation is added in the fermentation liquid obtained, each combined desulfurization B device
Thiobacillus bacterium solution；
Step 5 is added without iron containing compounds with No. A0 A device and makees blank test, and the A device of A1-A6 sequentially adds
FeCl2Amount be 0.16mmol, 0.32 mmol, 0.64 mmol, 0.96 mmol, 1.28mmol, 2.56 mmolFeCl2；It carries out
Reaction reacts 6 days, and records the variation of concentration of hydrogen sulfide.It the results are shown in Table 1.
Step 6 is added without iron containing compounds with No. B0 A device, and B device is inoculated with 3% ~ 5% Acidithiobacillus caldus bacterium solution
Make blank test, the A device of B1-B6 sequentially adds FeCl2Amount be 0.16mmol, 0.32 mmol, 0.64 mmol, 0.96
mmol、1.28mmol、2.56 mmolFeCl2, B device be successively inoculated with 3% ~ 5% Acidithiobacillus caldus bacterium solution carry out combined removal
The experiment of hydrogen sulfide in methane；
Step 7, it is 40 DEG C of temperature, to be reacted in 170 r/min shaking tables that desulfurizer, which is put into revolving speed, reaction 6
It, and record the variation of concentration of hydrogen sulfide.It the results are shown in Table 2.
Table 1: different proportion FeCl is only added2The change curve of concentration of hydrogen sulfide
| d | A0 | A1 | A2 | A3 | A4 | A5 | A6 |
| 1 | 1423.05 | 144.85 | 109.13 | 228.56 | 258.05 | 168.18 | 132.24 |
| 2 | 1541.64 | 198.09 | 95.07 | 251.99 | 241.64 | 155.70 | 110.31 |
| 3 | 1238.58 | 159.18 | 81.15 | 187.76 | 238.58 | 119.95 | 98.04 |
| 4 | 658.82 | 118.93 | 69.71 | 159.65 | 198.82 | 89.98 | 85.88 |
| 5 | 555.41 | 98.52 | 58.96 | 147.06 | 185.41 | 73.98 | 72.91 |
| 6 | 477.88 | 76.82 | 37.53 | 92.47 | 167.88 | 61.43 | 54.72 |
Being added without iron containing compounds concentration of hydrogen sulfide as can be drawn from Table 1 is 1423.05 ppm, only adds FeCl2Concentration
Concentration for 2 mM, 4 mM, 8 mM, 12 mM, 16 mM, 32 first day hydrogen sulfide in methane of mM is respectively
144.85ppm, 109.13ppm, 228.56ppm, 258.05ppm, 168.18ppm, 132.24ppm illustrate to add FeCl2As
Desulfurizing agent is feasible.
Table 2: different proportion FeCl is added2With the change curve of Acidithiobacillus caldus combined desulfurization concentration of hydrogen sulfide
| d | B0 | B1 | B2 | B3 | B4 | B5 | B6 |
| 1 | 22.41 | 6.32 | 4.81 | 3.16 | 2.44 | 3.03 | 3.43 |
| 2 | 25.06 | 4.74 | 4.02 | 0.86 | 0.59 | 3.43 | 0.99 |
| 3 | 19.29 | 3.69 | 2.11 | 0.49 | 0.34 | 0.99 | 0.49 |
| 4 | 15.12 | 2.70 | 0.79 | 0.32 | 0.23 | 0.59 | 0.35 |
| 5 | 8.59 | 1.38 | 0.59 | 0.09 | 0.10 | 0.17 | 0.30 |
| 6 | 5.93 | 0.72 | 0.33 | 0.17 | 0.13 | 0.24 | 0.24 |
Various concentration FeCl as can be drawn from Table 22Combined desulfurization is carried out with Acidithiobacillus caldus strain, wherein A device is not
It is higher that concentration of hydrogen sulfide in the blank test of iron containing compounds B device 3% ~ 5% Acidithiobacillus caldus bacterium solution of inoculation is added, highest
Up to 25.06ppm, when the FeCl of 2mM is added in A device2, B device 3% ~ 5% Acidithiobacillus caldus bacterium solution of inoculation, first day sulphur
Change hydrogen concentration and be reduced to 6.32ppm, illustrates the FeCl that various concentration is added2Combined removal is carried out with Acidithiobacillus caldus strain is added
Hydrogen sulfide in methane significant effect.
Embodiment 2
The present embodiment provides a kind of Fe (OH) that various concentration is added3On-line desulphurization and be added Acidithiobacillus caldus strain
Biological desulphurization carry out combined removal hydrogen sulfide in methane experiment.
Step 1, takes 7 groups of desulfurizers, number C0 to C6, and the resulting fermentation of 80mL step 2 is added in each desulfurization A device
Liquid；
Step 2, takes 7 groups of combined desulfurization devices, number D0 to D6, and 80mL embodiment 1 is added in each combined desulfurization A device
The 9K culture medium of 80mL is added in the resulting fermentation liquid of step 2, each combined desulfurization B device, is inoculated with 3% ~ 5% embodiment, 1 step 1
Resulting Acidithiobacillus caldus bacterium solution；
Step 3 is added without iron containing compounds with No. C0 A device and makees blank test, and the A device of C1-C6 sequentially adds Fe
(OH)3Amount be 0.16mmol, 0.32 mmol, 0.64 mmol, 0.96 mmol, 1.28mmol, 2.56 mmol Fe (OH)3；
It is reacted, reacts 6 days, and record the variation of concentration of hydrogen sulfide, the results are shown in Table 3.
Step 4 is added without iron containing compounds with No. D0 A device, and B device is inoculated with 3% ~ 5% Acidithiobacillus caldus bacterium solution
Make blank test, the A device of D1-D6 sequentially adds Fe (OH)3Amount be 0.16mmol, 0.32 mmol, 0.64 mmol, 0.96
mmol、1.28mmol、2.56 mmolFe(OH)3, B device is successively inoculated with 3% ~ 5% Acidithiobacillus caldus bacterium solution and combine
Except the experiment of hydrogen sulfide in methane；
Step 5, it is 40 DEG C of temperature, to be reacted in 170 r/min shaking tables that desulfurizer, which is put into revolving speed, reaction 6
It, and the variation of concentration of hydrogen sulfide is recorded, it the results are shown in Table 4.
Table 3: different proportion mixing Fe (OH) only is added3The change curve of concentration of hydrogen sulfide
| d | C0 | C1 | C2 | C3 | C4 | C5 | C6 |
| 1 | 1423.05 | 276.70 | 200.78 | 331.38 | 228.56 | 138.35 | 283.29 |
| 2 | 1541.64 | 380.04 | 174.78 | 674.58 | 631.99 | 569.17 | 556.47 |
| 3 | 1238.58 | 670.35 | 168.52 | 367.29 | 527.76 | 480.94 | 112.00 |
| 4 | 658.82 | 355.41 | 156.91 | 61.27 | 309.65 | 230.59 | 224.00 |
| 5 | 555.41 | 288.71 | 148.32 | 243.76 | 227.06 | 132.28 | 118.59 |
| 6 | 477.88 | 217.41 | 137.52 | 59.29 | 72.47 | 111.58 | 115.20 |
It is 1423.05 ppm that control sample, which is added without iron containing compounds and carries out the concentration of hydrogen sulfide of desulfurization, as can be drawn from Table 3,
Only add Fe (OH)3Amount be 0.16mmol, 0.32 mmol, 0.64 mmol, 0.96 mmol, 1.28mmol, 2.56 mmol
Fe(OH)3, the concentration of first day hydrogen sulfide in methane be respectively 276.7ppm, 200.78ppm, 331.38ppm,
228.56ppm, 138.35ppm, 283.29ppm illustrate to add Fe (OH)3It is feasible as desulfurizing agent.
Table 4: it is added different proportion Fe (OH)3With the change curve of Acidithiobacillus caldus combined desulfurization concentration of hydrogen sulfide
| d | D0 | D1 | D2 | D3 | D4 | D5 | D6 |
| 1 | 22.41 | 5.73 | 4.28 | 2.83 | 2.11 | 1.38 | 1.05 |
| 2 | 25.06 | 4.28 | 1.71 | 2.11 | 1.65 | 0.79 | 0.59 |
| 3 | 19.29 | 3.43 | 0.72 | 1.05 | 0.59 | 0.44 | 0.26 |
| 4 | 15.12 | 2.90 | 2.04 | 0.79 | 0.53 | 0.26 | 0.13 |
| 5 | 8.59 | 1.78 | 1.38 | 1.19 | 0.46 | 0.13 | 0.06 |
| 6 | 5.93 | 1.65 | 1.05 | 0.66 | 0.33 | 0.07 | 0.04 |
A device is added without iron containing compounds B device and is inoculated with 3% ~ 5% Acidithiobacillus caldus bacterium solution as can be drawn from Table 4
Concentration of hydrogen sulfide is higher in blank test, reaches as high as 25.06ppm, is added various concentration Fe (OH)3Afterwards carry out on-line desulphurization and
The biological desulphurization that Acidithiobacillus caldus strain is added carries out the concentration of first day D1-D6 device hydrogen sulfide of combined desulfurization and is respectively
5.73ppm, 4.28ppm, 2.83ppm, 2.11ppm, 1.38ppm, 1.05ppm illustrate the Fe (OH) that various concentration is added3Online
Desulfurization and the biological desulphurization that Acidithiobacillus caldus strain is added carry out combined removal hydrogen sulfide in methane significant effect.
Embodiment 3
The present embodiment provides a kind of Fe (OH)3、FeCl2And FeCl3On-line desulphurization and addition happiness according to different proportion mixing
The biological desulphurization of warm thiobacillus ferrooxidans' strain carries out the experiment of combined removal hydrogen sulfide in methane.
Step 1, takes 8 groups of desulfurizers, number E0 to E7, and the resulting fermentation of 80mL step 2 is added in each desulfurization A device
Liquid；
Step 2, takes 8 groups of combined desulfurization devices, number F0 to F7, and 80mL embodiment 1 is added in each combined desulfurization A device
The 9K culture medium of 80mL is added in the resulting fermentation liquid of step 2, each combined desulfurization B device, is inoculated with 3% ~ 5% embodiment, 1 step 1
Resulting Acidithiobacillus caldus bacterium solution；
Step 3 is added without iron containing compounds with No. E0 A device and makees blank test, and the A device of E1-E7 sequentially adds
2.88 mmol FeCl2、0.96mmol FeCl3、0.96 mmol Fe(OH)3、FeCl2:FeCl3=3:1(molar ratio, compares below
Example be molar ratio), FeCl2: FeCl3: Fe(OH)3=3:1:1、FeCl2: Fe(OH)3=3:1、FeCl3: Fe(OH)3=1:
1；It is reacted, reacts 6 days, and record the variation of concentration of hydrogen sulfide, the results are shown in Table 5.
Step 4 is added without iron containing compounds with No. F0 A device, and B device is inoculated with 3% ~ 5% Acidithiobacillus caldus bacterium solution
Make blank test, the A device of F1-F7 sequentially adds 2.88 mmol FeCl2、0.96mmol FeCl3、0.96 mmolFe
(OH)3、FeCl2:FeCl3=3:1、FeCl2: FeCl3: Fe(OH)3=3:1:1、FeCl2: Fe(OH)3=3:1、FeCl3: Fe
(OH)3=1:1, B device are successively inoculated with the experiment that 3% ~ 5% Acidithiobacillus caldus bacterium solution carries out combined removal hydrogen sulfide in methane；
Step 5, it is 40 DEG C of temperature, to be reacted in 170 r/min shaking tables that desulfurizer, which is put into revolving speed, reaction 6
It, and the result of variations for recording concentration of hydrogen sulfide is shown in Table 5.
Table 5: different proportion mixing Fe (OH) only is added3、FeCl2、FeCl3The change curve of concentration of hydrogen sulfide；
| d | E0 | E1 | E2 | E3 | E4 | E5 | E6 | E7 |
| 1 | 1423.05 | 358.05 | 550.98 | 228.56 | 198.09 | 109.18 | 172.24 | 139.13 |
| 2 | 1541.64 | 541.64 | 438.57 | 331.99 | 134.85 | 89.70 | 150.31 | 125.07 |
| 3 | 1238.58 | 438.58 | 335.79 | 227.76 | 109.18 | 79.95 | 138.04 | 111.15 |
| 4 | 658.82 | 358.82 | 325.92 | 209.65 | 97.93 | 66.98 | 115.88 | 99.71 |
| 5 | 555.41 | 235.41 | 290.19 | 187.06 | 82.52 | 53.98 | 92.91 | 88.96 |
| 6 | 477.88 | 127.88 | 118.57 | 72.47 | 76.82 | 41.43 | 60.72 | 77.53 |
It is 1423.05 ppm that control sample, which is added without iron containing compounds and carries out the concentration of hydrogen sulfide of desulfurization, as can be drawn from Table 5,
2.88 mmol FeCl are only added2、0.96mmol FeCl3、0.96 mmol Fe(OH)3、FeCl2:FeCl3=3:1、FeCl2:
FeCl3: Fe(OH)3=3:1:1、FeCl2: Fe(OH)3=3:1、FeCl3: Fe(OH)3The iron content of the different proportion mixing of=1:1
The concentration of first day hydrogen sulfide in methane of compound is respectively 358.05 ppm, 550.98 ppm, 228.56 ppm, 198.09
ppm、109.18 ppm、172.24 ppm、139.13 ppm。
Table 6: it is added different proportion mixing Fe (OH)3、FeCl2、FeCl3With addition Acidithiobacillus caldus combined desulfurization work
The change curve of the concentration of hydrogen sulfide of skill.
| F0 | F1 | F2 | F3 | F4 | F5 | F6 | F7 | |
| 1 | 22.41 | 2.57 | 3.01 | 2.24 | 1.19 | 1.45 | 1.19 | 0.79 |
| 2 | 25.06 | 1.32 | 2.37 | 0.72 | 0.92 | 0.72 | 0.86 | 0.59 |
| 3 | 19.29 | 0.66 | 0.99 | 0.66 | 0.66 | 0.53 | 0.40 | 0.20 |
| 4 | 15.12 | 0.59 | 0.86 | 0.60 | 0.59 | 0.40 | 0.20 | 0.07 |
| 5 | 8.59 | 0.54 | 0.61 | 0.53 | 0.53 | 0.28 | 0.07 | 0.06 |
| 6 | 5.93 | 0.51 | 0.14 | 0.48 | 0.26 | 0.07 | 0.05 | 0.03 |
The concentration of hydrogen sulfide is down to 5.93 ppm, combined desulfurization first from 25.06 ppm in control group as can be drawn from Table 6
The concentration of its F1-F7 device hydrogen sulfide be respectively 2.57ppm, 3.01ppm, 2.24ppm, 1.19ppm, 1.45ppm, 1.19ppm,
0.79ppm, it is seen then that combined desulfurization technique decreased significantly the content of hydrogen sulfide, and the removal effect of hydrogen sulfide is relatively good.
Claims (3)
1. a kind of method of iron containing compounds and Acidithiobacillus caldus combined removal hydrogen sulfide in methane, which is characterized in that packet
Include following steps:
1) iron containing compounds desulfurization: iron containing compounds are added in the reactor for producing biogas with charging, are fermented in marsh gas raw materials
While carry out iron containing compounds desulfurization；
2) biological desulphurization: the biogas after step 1) iron containing compounds desulfurization is passed into the fermentation liquid of Acidithiobacillus caldus,
Detect the rear collection up to standard of hydrogen sulfide in methane content；
Wherein: the concentration of the iron containing compounds in the reactor is 2mM ~ 32mM；The marsh gas raw materials are organic wastewater, livestock and poultry
At least one of excrement, house refuse or stalk；In the fermentation liquid of the Acidithiobacillus caldus viable count be 2.0 ×
106A/mL ~ 10.0 × 106A/mL;
Iron containing compounds described in step 1) are the mixing of one or more of frerrous chloride, iron chloride or iron hydroxide;
Acidithiobacillus caldus described in step 2 is that the bacterium numbering of Chinese microorganism strain collection preservation is 1.7296
Bacterial strain;
The culture medium prescription of Acidithiobacillus caldus described in step 2 includes component A and component B, wherein component A are as follows: ammonium sulfate
3.0 g, 0.1 g of potassium chloride, 0.5 g of dipotassium hydrogen phosphate, 0.5 g of epsom salt, calcium nitrate 0.01 g, distilled water 1L, use are dilute
PH is adjusted to 2.5 by sulfuric acid, high pressure sterilization 20min;B component are as follows: ferrous sulfate 3 ~ 4%, distilled water 10mL cross film degerming;Before inoculation
B component is added in component A and is mixed to get culture medium.
2. the side of iron containing compounds according to claim 1 and Acidithiobacillus caldus combined removal hydrogen sulfide in methane
Method, which is characterized in that the condition of culture of Acidithiobacillus caldus described in step 2 is that revolving speed is 170 r/min, temperature 40 ~ 45
The culture medium prescription of Acidithiobacillus caldus described in DEG C step 2 includes component A and component B, wherein component A are as follows: ammonium sulfate
3.0 g, 0.1 g of potassium chloride, 0.5 g of dipotassium hydrogen phosphate, 0.5 g of epsom salt, calcium nitrate 0.01 g, distilled water 1L, use are dilute
PH is adjusted to 2.5 by sulfuric acid, high pressure sterilization 20min;B component are as follows: ferrous sulfate 3 ~ 4%, distilled water 10mL cross film degerming;Before inoculation
B component is added in component A and is mixed to get culture medium.
3. the side of iron containing compounds according to claim 1 and Acidithiobacillus caldus combined removal hydrogen sulfide in methane
Method, which is characterized in that the iron containing compounds are FeCl2: FeCl3: Fe(OH)3The mixture of 3:1:1 in molar ratio.
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