CN106554837A - Method for removing hydrogen sulfide in biogas by combining iron-containing compound and Acidithiobacillus caldus - Google Patents
Method for removing hydrogen sulfide in biogas by combining iron-containing compound and Acidithiobacillus caldus Download PDFInfo
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- CN106554837A CN106554837A CN201611010793.0A CN201611010793A CN106554837A CN 106554837 A CN106554837 A CN 106554837A CN 201611010793 A CN201611010793 A CN 201611010793A CN 106554837 A CN106554837 A CN 106554837A
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- China
- Prior art keywords
- hydrogen sulfide
- acidithiobacillus caldus
- iron containing
- containing compoundses
- biogas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 113
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 73
- 241001464929 Acidithiobacillus caldus Species 0.000 title claims abstract description 63
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 title abstract description 6
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 45
- 230000023556 desulfurization Effects 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 68
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 19
- 239000012530 fluid Substances 0.000 claims description 16
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 14
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 230000001580 bacterial effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000001963 growth medium Substances 0.000 claims description 4
- 238000011081 inoculation Methods 0.000 claims description 4
- 244000005700 microbiome Species 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 210000003608 fece Anatomy 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- 244000144972 livestock Species 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 244000144977 poultry Species 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 7
- 230000003009 desulfurizing effect Effects 0.000 abstract description 5
- 238000000855 fermentation Methods 0.000 abstract description 4
- 230000004151 fermentation Effects 0.000 abstract description 4
- 150000002506 iron compounds Chemical class 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- 241000894006 Bacteria Species 0.000 description 13
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 235000015097 nutrients Nutrition 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000002054 inoculum Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000605118 Thiobacillus Species 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012549 training Methods 0.000 description 3
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 2
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- -1 steam Inorganic materials 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 241000266272 Acidithiobacillus Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010020056 Hydrogenase Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000004379 membrane Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000007269 microbial metabolism Effects 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 231100000189 neurotoxic Toxicity 0.000 description 1
- 230000002887 neurotoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 210000001082 somatic cell Anatomy 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000004174 sulfur cycle Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/05—Biogas
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Genetics & Genomics (AREA)
- Biotechnology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Environmental & Geological Engineering (AREA)
- Microbiology (AREA)
- General Health & Medical Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Medicinal Chemistry (AREA)
- Tropical Medicine & Parasitology (AREA)
- Virology (AREA)
- Gas Separation By Absorption (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method for jointly removing hydrogen sulfide in biogas by using an iron-containing compound and Acidithiobacillus caldus, which comprises the following steps: 1) desulfurization of iron-containing compounds: adding the iron-containing compound into a reactor for producing biogas along with the feed, and desulfurizing the iron-containing compound while fermenting the biogas raw material; 2) biological desulfurization: and (2) introducing the desulfurized biogas containing the iron compounds in the step 1) into a fermentation liquid of Acidithiobacillus caldus, and collecting the biogas after the content of hydrogen sulfide in the biogas reaches the standard. The removal efficiency is high, and the cost and the workload of subsequent desulfurization are reduced. After the combined removal, the content of hydrogen sulfide in the biogas is lower than 5ppm, preferably lower than 1ppm, and the hydrogen sulfide is basically and completely removed.
Description
Technical field
The invention belongs to bioenergy technical field, and in particular to a kind of iron containing compoundses and Acidithiobacillus caldus joint
The method for removing hydrogen sulfide in methane.
Background technology
With rapid development of economy, demand for energy increasingly rises all over the world.In energy resource structure, with oil, coal
Fossil energy based on charcoal etc. remains unchanged in occupation of the principal status of public economy, if the mankind too rely on these traditional fossil energies, which can not be again
Natural disposition will cause energy crisis.Biogas gradually causes the attention of people as a kind of emerging green energy resource.Biogas is a kind of
Mixed gas, typically containing CH4For 60% ~ 70%, CO2For 30% ~ 40%, a small amount of H2S, steam, NH3Deng.Wherein hydrogen sulfide is to the person
Safety, environment and equipment have larger harm.For personal safety, hydrogen sulfide has stronger stimulation, is to mucous membrane
Strong neurotoxic substance.For environment, hydrogen sulfide has pollution to water body and air, and the sulfur dioxide for producing that burns causes
The generation of acid rain.For equipment, there is corrosion harmfulness in oil extraction, deposit transport and process, weight can be seriously caused
Big security incident.Biogas purposes is different, to H2The requirement of S contents is also different, and respective country and professional standard specify：If utilizing natural pond
Gas generates electricity, then H2The concentration of S need to be less than or equal to 200 ~ 300mg/m3；If using biogas is 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 not pre-processed, the H contained in biogas2S can corrode metallic conduit, instrument and meter etc..Therefore, biogas is in synthesis
H must be carried out using before2S is removed.
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, by the specific solvent such as NaOH, ammoniacal liquor, to react to remove sulfuration with hydrogen sulfide
A kind of method of hydrogen, reaches recycling for solvent by effect of the oxygen to solvent.Due to the flow velocity and flow of NaOH
Impact, hydrogen sulfide can not be dissolved completely in wherein, and thiosulfate can be produced in course of dissolution, and these are all by shadow
Desulfurized effect is rung, and also has the problems such as investment is more, operational management is complicated, desulphurization cost is high and absorbing liquid need to be changed.Dry method takes off
Sulphur is that one kind utilizes oxygen, with iron oxide as oxidant by Oxidation of Hydrogen Sulfide as elemental sulfur or sulfide a kind of desulfurization side
Formula.Elemental sulfur serves the effect of a catalysis in absorption process.But desulfurization by dry method has, and installation area is big, operation
Discontinuously, desulfurizing agent is difficult to regenerate, is difficult to change and the low problem of desulfuration efficiency.Biological desulfurizing technology is by 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 easily subject to environment temperature
The impact of degree.
Acidithiobacillus caldus (Acidithiobacillus caldus) it is thiobacillus ferrooxidans' category
(Acidithiobacillus) in only appropriate Thermophilic Bacteria, acidophilus is aerobic, is a kind of chemoautotrophic Gram-negative bacteria,
Originate by energy of the sulfide of sulphur or reproducibility, with the CO in air2For carbon source, and the inorganic nutrient substance such as absorbed nitrogen, phosphorus
Synthesis somatic cells, typically can be by sulphur powder, HS-And H2S is oxidized to H2SO4.Li Yaxin etc. is biological by aerobic colorless sulfur bacteria
Membrane reactor, has carried out the experiment that sulfide changes into elemental sulfur, and the clearance of hydrogen sulfide is up to 87%.
Fe in iron containing compoundses desulphurization reaction2+It is the important component of hydrogenase etc. in sulfate reducing bacteria body, while also can
SO is reduced with which4 2-During the S that produces2-Form the minimum FeS precipitations of solubility product.Due to Fe2+Addition, promote it is various
The synthesis of enzyme, ultimately resulting in the sulfide content in system reduces even eliminating.This aspect is possibly due to Fe3+Can convert
For Fe2+, i.e. Fe3+With S2-Generation redox reaction generates Fe2+；Another aspect cell interior Fe2+As the activity of enzyme
Based component is also mutually to be converted by itself valence state and realize that place enzyme transmits the effect of electronics.
The content of the invention
It is an object of the invention to provide a kind of iron containing compoundses and Acidithiobacillus caldus combined removal hydrogen sulfide in methane
Method, with easy to operate, technological process is simple, improves utilization of resources value, saves expense, to improve desulfuration efficiency etc. excellent
Point, can remove the hydrogen sulfide in biogas with stability and high efficiency, it will help improve biogas utilization level, break through biogas desulfurization difficult
Topic.
To achieve these goals, the technical solution adopted in the present invention is：
A kind of method of iron containing compoundses and Acidithiobacillus caldus combined removal hydrogen sulfide in methane, comprises the steps：
1）Iron containing compoundses desulfurization：Iron containing compoundses are added to charging in the reactor for producing biogas, are fermented in marsh gas raw materials
While carry out iron containing compoundses desulfurization；
2）Biological desulphurization：By step 1）Biogas after iron containing compoundses desulfurization is passed in the zymotic fluid of Acidithiobacillus caldus,
Collect after detection hydrogen sulfide in methane content is up to standard.
Step 1）Described in iron containing compoundses be one or more mixed in frerrous chloride, iron chloride or iron hydroxide
Close.It is preferred that FeCl2: FeCl3: Fe(OH)3=3:1:1。
Step 1）Concentration of the iron containing compoundses in biogas fermentation reactor is 2mM ~ 32mM.It is preferred that iron content chemical combination
The concentration of thing is 32mM.
The marsh gas raw materials are at least one in 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 are the bacterium that the bacterium numbering of Chinese microorganism strain collection preservation is 1.7296
Strain.
Step 2）Described in Acidithiobacillus caldus zymotic fluid in viable count be 2.0 × 106Individual/mL ~ 10.0 × 106
Individual/mL.
Step 2）Described in Acidithiobacillus caldus condition of culture be rotating speed be 170 r/min, 40 ~ 45 DEG C of temperature.
Step 2）Described in Acidithiobacillus caldus culture medium be 9K culture mediums, filling a prescription is：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, 0.01 g of calcium nitrate, distilled water 1L, with dilute sulfuric acid by pH
2.5 are adjusted to, autoclaving 20min.B：Ferrous sulfate 3 ~ 4%, distilled water 10mL cross film degerming.B is added to into A cultures before inoculation
In base.
The Acidithiobacillus caldus are 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 class obligate autotrophy, extensively
It is general to be distributed in Sulphide Ore, acid mine water and soil, send out at aspects such as bacterial metallurgy, the desulfurization of coal and the process of sulfur-containing waste water
Important function is waved, while also occupying critical role in the sulfur cycle of nature.Dopson and Lindtrom have researched and analysed happiness
The metabolin of warm thiobacillus ferrooxidans has the effect of surfactant, element sulphur is fully dissolved.The warm acidophilus sulphur bar of happiness
Bacterium oxidability is very strong, and cell increases the elemental sulfur that 1g just can generate more than 20g.By step 1）Biogas after desulfurization in situ is continuous
Be passed in the zymotic fluid of Acidithiobacillus caldus, according to the consumption for being passed through rate adaptation zymotic fluid of biogas, with what is collected
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 is：Acidithiobacillus caldus bacterial strain is carried out into renewal cultivation, is drawn with aseptic straw
The 9K culture mediums of 0.3 ~ 0.5mL, instill in ampoule, gently shake, and make lyophilized thalline dissolving in suspension, draw whole bacterium and hang
Liquid, moves in the 9K culture mediums of 5mL, puts 170 r/min of mixing speed, 40 ~ 45 DEG C of 48 ~ 72h of culture of temperature, as bacterial classification is passed through
After freeze-drying is preserved, period of delay is longer, and the Acidithiobacillus caldus nutrient solution of generation renewal cultivation is pressed 3% ~ 5% inoculum concentration
It is inoculated in 5mL fluid nutrient mediums, same condition of culture carries out double squamous subculture, will be the happiness temperature of renewal cultivation thermophilic
Sour Thiobacillus nutrient solution is inoculated in 80mL fluid nutrient mediums by 3% ~ 5% inoculum concentration, and same condition of culture will like warm acidophilus
Thiobacillus is cultivated to logarithmic phase mid-term（4~5d）.
Desulfurization is carried out during biogas to be passed into the zymotic fluid of Acidithiobacillus caldus, sweetening process controls mixing speed and is
170 r/min, 40 ~ 45 DEG C of temperature.
The iron containing compoundses adopt solid or liquid.
The good effect that the present invention has is：As the present invention is combined using iron containing compoundses and Acidithiobacillus caldus
Sulfur removal technology removes the hydrogen sulfide in biogas, and iron containing compoundses are directly added in marsh gas reactor with charging and carry out desulfurization first,
Then the biogas for producing is entered in the B devices equipped with 9K culture mediums and 3% ~ 5% Acidithiobacillus caldus inoculum concentration, so as to realize
On-line desulphurization and biological desulphurization carry out combined removal hydrogen sulfide in methane, so as to significantly reduce hydrogen sulfide in in-situ biogas
Amount, removing have the hydrogen sulfide of harm to environment and equipment, and removal efficiency is high, reduces the expense and workload of follow-up desulfurization.
After joint removing, hydrogen sulfide in methane content is less than 5ppm, more excellent less than 1ppm, substantially completely removes.
Description of the drawings
Fig. 1 is reaction unit figure.
Specific embodiment
Below in conjunction with the accompanying drawings, specific embodiments of the present invention is described in detail.
Acidithiobacillus caldus are 1.7296 by Chinese microorganism strain collection preservation, bacterium numbering.Hereinafter implement
Organic wastewater is adopted in example as the raw material of biogas production.
Embodiment 1
The present embodiment provides a kind of FeCl for adding variable concentrations2On-line desulphurization and add Acidithiobacillus caldus strain biology
Desulfurization carries out the experiment of combined removal hydrogen sulfide in methane.
Acidithiobacillus caldus bacterial strain is carried out renewal cultivation by step one, draws the 9K trainings of 0.3 ~ 0.5mL with aseptic straw
Foster base, instills in ampoule, gently shakes, and makes lyophilized thalline dissolving in suspension, draws whole bacteria suspensions, moves to the 9K trainings of 5mL
In foster base, 170 r/min of mixing speed, 40 ~ 45 DEG C of 48 ~ 72h of culture of temperature are put, as bacterial classification is after freeze-drying preservation,
Period of delay is longer, and the Acidithiobacillus caldus nutrient solution of generation renewal cultivation is inoculated into the training of 5mL liquid by 3% ~ 5% inoculum concentration
In foster base, same condition of culture carries out double squamous subculture, by the Acidithiobacillus caldus nutrient solution of renewal cultivation
It is inoculated in 80mL fluid nutrient mediums by 3% ~ 5% inoculum concentration, same condition of culture is by Acidithiobacillus caldus culture to right
The number interim phase（4~5d）.The culture medium prescription of Acidithiobacillus caldus is：A：3.0 g of ammonium sulfate, 0.1 g of potassium chloride, phosphoric acid hydrogen
0.5 g of dipotassium, 0.5 g of epsom salt, pH is adjusted to 2.5 with dilute sulfuric acid, autoclaving by 0.01 g of calcium nitrate, distilled water 1L
20min.B：Ferrous sulfate 3 ~ 4%, distilled water 10mL cross film degerming.B is added in A culture mediums before inoculation.
Step 2, using alcohol waste water COD（COD）Be 29,000mg/L, pH be 3.78, total nitrogen is
74.84mg/L, general volatile aliphatic acid（VFAs）It is 21.45 mM, activated sludge volatile suspended solid VSS（36.49 g
/L）Zymotic fluid, the zymotic fluid is used as the raw material for forming methane；
Step 3, takes 7 groups of desulfurizers, and numbering A0 to A6, each desulfurization A device adds the zymotic fluid obtained by 80mL step 2；
Step 4, takes 7 groups of combined desulfurization devices, and numbering B0 to B6, each combined desulfurization A device is added obtained by 80mL step 2
Zymotic fluid, each combined desulfurization B devices add the 9K culture mediums of 80mL, the happiness temperature acidophilus sulphur bar being inoculated with obtained by 3% ~ 5% step one
Bacterium bacterium solution；
Step 5, is added without iron containing compoundses with the A devices of No. A0 and makees blank test, and the A devices of A1-A6 sequentially add FeCl2
Amount be 0.16mmol, 0.32 mmol, 0.64 mmol, 0.96 mmol, 1.28mmol, 2.56 mmolFeCl2；Carry out anti-
Should, react 6 days, and record the change of concentration of hydrogen sulfide.The results are shown in Table 1.
Step 6, is added without iron containing compoundses with the A devices of No. B0, and B devices are inoculated with 3% ~ 5% Acidithiobacillus caldus bacterium solution
Make blank test, the A devices of B1-B6 sequentially add FeCl2Amount be 0.16mmol, 0.32 mmol, 0.64 mmol, 0.96
mmol、1.28mmol、2.56 mmolFeCl2, B devices are inoculated with 3% ~ 5% Acidithiobacillus caldus bacterium solution successively and carry out combined removal
The experiment of hydrogen sulfide in methane；
Desulfurizer is put into rotating speed for, in 170 r/min shaking tables, 40 DEG C of temperature is reacted, is reacted 6 days by step 7, and
The change of record concentration of hydrogen sulfide.The results are shown in Table 2.
Table 1：Different proportion FeCl is added only2The 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 |
It is 1423.05 ppm to be added without iron containing compoundses concentration of hydrogen sulfide as can be drawn from Table 1, only adds FeCl2Concentration is 2
MM, 4 mM, 8 mM, 12 mM, 16 mM, the 32 mM hydrogen sulfide in methane of first day concentration be respectively 144.85ppm,
109.13ppm, 228.56ppm, 258.05ppm, 168.18ppm, 132.24ppm, illustrate to add FeCl2As desulfurizing agent being can
Capable.
Table 2：Add different proportion FeCl2With 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 |
Variable concentrations FeCl as can be drawn from Table 22Combined desulfurization is carried out with Acidithiobacillus caldus strain, wherein A devices are added without
During iron containing compoundses B devices are inoculated with the blank test of 3% ~ 5% Acidithiobacillus caldus bacterium solution, concentration of hydrogen sulfide is higher, reaches as high as
25.06ppm, when A devices add the FeCl of 2mM2, B devices 3% ~ 5% Acidithiobacillus caldus bacterium solution of inoculation, first day hydrogen sulfide
Concentration is reduced to 6.32ppm, illustrates to add the FeCl of variable concentrations2Combined removal biogas is carried out with addition Acidithiobacillus caldus strain
Middle hydrogen sulfide effect is significant.
Embodiment 2
The present embodiment provides a kind of Fe (OH) for adding variable concentrations3On-line desulphurization and add Acidithiobacillus caldus strain life
Thing desulfurization carries out the experiment of combined removal hydrogen sulfide in methane.
Step one, takes 7 groups of desulfurizers, and numbering C0 to C6, each desulfurization A device adds the fermentation obtained by 80mL step 2
Liquid；
Step 2, takes 7 groups of combined desulfurization devices, and numbering D0 to D6, each combined desulfurization A device adds 1 step of 80mL embodiments
Zymotic fluid obtained by two, each combined desulfurization B devices add the 9K culture mediums of 80mL, are inoculated with obtained by 3% ~ 5% embodiment, 1 step one
Acidithiobacillus caldus bacterium solution；
Step 3, is added without iron containing compoundses with the A devices of No. C0 and makees blank test, and the A devices of C1-C6 sequentially add Fe
(OH)3Amount be 0.16mmol, 0.32 mmol, 0.64 mmol, 0.96 mmol, 1.28mmol, 2.56 mmol Fe (OH)3；
Reacted, reacted 6 days, and recorded the change of concentration of hydrogen sulfide, the results are shown in Table 3.
Step 4, is added without iron containing compoundses with the A devices of No. D0, and B devices are inoculated with 3% ~ 5% Acidithiobacillus caldus bacterium solution
Make blank test, the A devices of D1-D6 sequentially add Fe (OH)3Amount be 0.16mmol, 0.32 mmol, 0.64 mmol, 0.96
mmol、1.28mmol、2.56 mmolFe(OH)3, B devices are inoculated with 3% ~ 5% Acidithiobacillus caldus bacterium solution successively and carry out combining
Except the experiment of hydrogen sulfide in methane；
Desulfurizer is put into rotating speed for, in 170 r/min shaking tables, 40 DEG C of temperature is reacted, is reacted 6 days by step 5, and
The change of record concentration of hydrogen sulfide, the results are shown in Table 4.
Table 3：Different proportion mixing Fe (OH) is added only3The 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 |
As can be drawn from Table 3 control sample be added without iron containing compoundses carry out desulfurization concentration of hydrogen sulfide be 1423.05 ppm, only throw
Plus 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 the hydrogen sulfide in methane of first day 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：Add 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 devices are added without the blank that iron containing compoundses B devices are inoculated with 3% ~ 5% Acidithiobacillus caldus bacterium solution as can be drawn from Table 4
In test, concentration of hydrogen sulfide is higher, reaches as high as 25.06ppm, adds variable concentrations Fe (OH)3After carry out on-line desulphurization and addition
The biological desulphurization of Acidithiobacillus caldus strain 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 to add the Fe (OH) of variable concentrations3Online
The biological desulphurization of desulfurization and addition Acidithiobacillus caldus strain carries out combined removal hydrogen sulfide in methane effect is significant.
Embodiment 3
The present embodiment provides a kind of Fe (OH)3、FeCl2And FeCl3The on-line desulphurization and addition happiness temperature mixed according to different proportion is thermophilic
The biological desulphurization of sour Thiobacillus strain carries out the experiment of combined removal hydrogen sulfide in methane.
Step one, takes 8 groups of desulfurizers, and numbering E0 to E7, each desulfurization A device adds the fermentation obtained by 80mL step 2
Liquid；
Step 2, takes 8 groups of combined desulfurization devices, and numbering F0 to F7, each combined desulfurization A device adds 1 step of 80mL embodiments
Zymotic fluid obtained by two, each combined desulfurization B devices add the 9K culture mediums of 80mL, are inoculated with obtained by 3% ~ 5% embodiment, 1 step one
Acidithiobacillus caldus bacterium solution；
Step 3, is added without iron containing compoundses with the A devices of No. E0 and makees blank test, and the A devices of E1-E7 sequentially add 2.88
mmol FeCl2、0.96mmol FeCl3、0.96 mmol Fe(OH)3、FeCl2:FeCl3=3:1（Mol ratio, following ratio are
Mol ratio）、FeCl2: FeCl3: Fe(OH)3=3:1:1、FeCl2: Fe(OH)3=3:1、FeCl3: Fe(OH)3=1:1；Carry out
Reaction, reacts 6 days, and records the change of concentration of hydrogen sulfide, the results are shown in Table 5.
Step 4, is added without iron containing compoundses with the A devices of No. F0, and B devices are inoculated with 3% ~ 5% Acidithiobacillus caldus bacterium solution
Make blank test, the A devices of F1-F7 sequentially add 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 is inoculated with 3% ~ 5% Acidithiobacillus caldus bacterium solution successively and carries out the experiment of combined removal hydrogen sulfide in methane；
Desulfurizer is put into rotating speed for, in 170 r/min shaking tables, 40 DEG C of temperature is reacted, is reacted 6 days by step 5, and
The result of variations of record concentration of hydrogen sulfide is shown in Table 5.
Table 5：Different proportion mixing Fe (OH) is added only3、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 |
As can be drawn from Table 5 control sample be added without iron containing compoundses carry out desulfurization concentration of hydrogen sulfide be 1423.05 ppm, only plus
Enter 2.88 mmol FeCl2、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)3=1:The iron content of 1 different proportion mixing
The concentration of first day hydrogen sulfide in methane of compound be respectively 358.05 ppm, 550.98 ppm, 228.56 ppm, 198.09
ppm、109.18 ppm、172.24 ppm、139.13 ppm。
Table 6:Add 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 |
In control group, the concentration of hydrogen sulfide is down to 5.93 ppm, combined desulfurization first from 25.06 ppm 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 is decreased obviously the content of hydrogen sulfide, and the removal effect of hydrogen sulfide is relatively good.
Claims (9)
1. a kind of method of iron containing compoundses and Acidithiobacillus caldus combined removal hydrogen sulfide in methane, it is characterised in that bag
Include following steps：
1）Iron containing compoundses desulfurization：Iron containing compoundses are added to charging in the reactor for producing biogas, are fermented in marsh gas raw materials
While carry out iron containing compoundses desulfurization；
2）Biological desulphurization：By step 1）Biogas after iron containing compoundses desulfurization is passed in the zymotic fluid of Acidithiobacillus caldus,
Collect after detection hydrogen sulfide in methane content is up to standard.
2. the side of iron containing compoundses according to claim 1 and Acidithiobacillus caldus combined removal hydrogen sulfide in methane
Method, it is characterised in that step 1）Described in iron containing compoundses be frerrous chloride, iron chloride or iron hydroxide in one kind or several
The mixing planted.
3. the side of iron containing compoundses according to claim 1 and Acidithiobacillus caldus combined removal hydrogen sulfide in methane
Method, it is characterised in that step 1）Iron containing compoundses concentration in the reactor is 2mM ~ 32mM.
4. the side of iron containing compoundses according to claim 1 and Acidithiobacillus caldus combined removal hydrogen sulfide in methane
Method, it is characterised in that step 1）Described in marsh gas raw materials be organic wastewater, feces of livestock and poultry, house refuse or stalk in extremely
Few one kind.
5. the side of iron containing compoundses according to claim 1 and Acidithiobacillus caldus combined removal hydrogen sulfide in methane
Method, it is characterised in that step 2）Described in Acidithiobacillus caldus for Chinese microorganism strain collection preservation bacterial classification compile
Number for 1.7296 bacterial strain.
6. the side of iron containing compoundses according to claim 1 and Acidithiobacillus caldus combined removal hydrogen sulfide in methane
Method, it is characterised in that step 2）Described in Acidithiobacillus caldus zymotic fluid in viable count be 2.0 × 106Individual/mL ~
10.0×106Individual/mL.
7. the side of iron containing compoundses according to claim 1 and Acidithiobacillus caldus combined removal hydrogen sulfide in methane
Method, it is characterised in that step 2）Described in Acidithiobacillus caldus condition of culture be rotating speed be 170 r/min, temperature 40 ~ 45
℃。
8. the side of iron containing compoundses according to claim 1 and Acidithiobacillus caldus combined removal hydrogen sulfide in methane
Method, it is characterised in that step 2）Described in the culture medium prescription of Acidithiobacillus caldus include component A and component B, wherein A groups
It is divided into：3.0 g of ammonium sulfate, 0.1 g of potassium chloride, 0.5 g of dipotassium hydrogen phosphate, 0.5 g of epsom salt, 0.01 g of calcium nitrate, steam
PH is adjusted to 2.5 with dilute sulfuric acid, autoclaving 20min by distilled water 1L;9. B component is：Ferrous sulfate 3 ~ 4%, distilled water 10mL,
Cross film degerming;B component is added in component A before inoculation and is mixed to get culture medium.
9. the side of iron containing compoundses according to claim 2 and Acidithiobacillus caldus combined removal hydrogen sulfide in methane
Method, it is characterised in that described iron containing compoundses are FeCl2: FeCl3: Fe(OH)3In molar ratio 3:1:1 mixture.
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| CN109456916A (en) * | 2018-11-21 | 2019-03-12 | 南开大学 | A kind of method that charcoal strengthens heavy metal in indigenous ferrous oxide removal of bacteria pig manure |
| CN109966910A (en) * | 2017-12-28 | 2019-07-05 | 许传高 | A kind of purification process of amino acid fermentation foul smell |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200698A (en) * | 2007-11-26 | 2008-06-18 | 宁波工程学院 | Microorganism synchronously removing ammonia and sulfureted hydrogen foul gas and method for preparing the same |
| CN101705126A (en) * | 2009-07-28 | 2010-05-12 | 北京合百意可再生能源技术有限公司 | In-situ biogas coupling type long-acting desulfurizer |
| CN101705249A (en) * | 2009-07-28 | 2010-05-12 | 北京合百意可再生能源技术有限公司 | High-value utilization process for in-situ biogas desulfurization comprehensive treatment |
-
2016
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200698A (en) * | 2007-11-26 | 2008-06-18 | 宁波工程学院 | Microorganism synchronously removing ammonia and sulfureted hydrogen foul gas and method for preparing the same |
| CN101705126A (en) * | 2009-07-28 | 2010-05-12 | 北京合百意可再生能源技术有限公司 | In-situ biogas coupling type long-acting desulfurizer |
| CN101705249A (en) * | 2009-07-28 | 2010-05-12 | 北京合百意可再生能源技术有限公司 | High-value utilization process for in-situ biogas desulfurization comprehensive treatment |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109966910A (en) * | 2017-12-28 | 2019-07-05 | 许传高 | A kind of purification process of amino acid fermentation foul smell |
| CN109456916A (en) * | 2018-11-21 | 2019-03-12 | 南开大学 | A kind of method that charcoal strengthens heavy metal in indigenous ferrous oxide removal of bacteria pig manure |
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