CN115121092A - Application of campylobacter xanthus in desulfurization - Google Patents

Application of campylobacter xanthus in desulfurization Download PDF

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CN115121092A
CN115121092A CN202210647185.XA CN202210647185A CN115121092A CN 115121092 A CN115121092 A CN 115121092A CN 202210647185 A CN202210647185 A CN 202210647185A CN 115121092 A CN115121092 A CN 115121092A
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gas
desulfurization
sulfur
campylobacter
regeneration
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CN115121092B (en
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魏雄辉
袁本雄
叶青保
冯家俊
周稳华
王跃发
李世嵩
户春
蒋俊华
张洪
汉春利
郑立华
占善亮
魏建国
刘家旭
袁冬秀
聂金鹏
魏子卿
万明金
李祥斌
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Beijing Hengtai Yuansheng High Tech Co ltd
Beijing Honglong Environmental Protection Co ltd
Beijing Boyuan Hengsheng High Technology Co Ltd
Jiangxi Yongfeng Boyuan Industrial Co Ltd
Tongling Pacific Special Material Ltd
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Beijing Hengtai Yuansheng High Tech Co ltd
Beijing Honglong Environmental Protection Co ltd
Beijing Boyuan Hengsheng High Technology Co Ltd
Jiangxi Yongfeng Boyuan Industrial Co Ltd
Tongling Pacific Special Material Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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 by absorption
    • B01D53/1456Removing acid components
    • B01D53/1468Removing hydrogen sulfide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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 by absorption
    • B01D53/1425Regeneration of liquid absorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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 by absorption
    • B01D53/1487Removing organic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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 by absorption
    • B01D53/1493Selection of liquid materials for use as absorbents
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/002Removal of contaminants
    • C10K1/003Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004Sulfur containing contaminants, e.g. hydrogen sulfide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L3/00Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10Working-up natural gas or synthetic natural gas
    • C10L3/101Removal of contaminants
    • C10L3/102Removal of contaminants of acid contaminants
    • C10L3/103Sulfur containing contaminants
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00Microorganisms, 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
    • C12N1/20Bacteria; Culture media therefor
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P3/00Preparation of elements or inorganic compounds except carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12RINDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
    • C12R2001/00Microorganisms ; Processes using microorganisms
    • C12R2001/01Bacteria or Actinomycetales ; using bacteria or Actinomycetales
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/30Fuel from waste, e.g. synthetic alcohol or diesel

Abstract

The invention provides an application of Campylobacter flavus in desulfurization of gas containing hydrogen sulfide and/or organic sulfur. The sulfur is hydrogen sulfide and/or organic sulfur in the sulfur-containing gas. The campylobacter flavus with the saliferous membrane has wide industrial application in the field of sulfur-containing gas desulfurization, can be used for desulfurization of natural gas, coke oven gas, oil field gas, blast furnace gas, city gas, gas, water gas, synthetic ammonia semi-water gas and conversion gas, synthetic waste gas of dye factories, waste gas of chemical fiber factories, biogas and other industrial raw material gases or waste gases containing hydrogen sulfide and organic sulfur, and the total sulfur content of the sulfur-containing gas is less than 99.9 percent. Not only can remove hydrogen sulfide in the organic sulfur, but also has certain removal capacity for organic sulfur. And the traditional wet desulphurization method can not keep high desulphurization efficiency economically for a long time, but the desulphurization method can keep high desulphurization efficiency economically for a long time because the halophilic membrane campylobacter flavus can be regenerated and used.

Description

Application of campylobacter xanthus in desulfurization
Technical Field
The invention relates to application of campylobacter xanthus in desulfurization.
Background
Due to the rapid development of the society, the large-scale exploitation of natural gas, coal mine, oil field gas and shale gas is driven; the widespread use of fossil fuels, such as coal and petroleum, has led to the large production of coke oven gas, coal gas, water gas, gas, synthetic ammonia semi-water gas and shift gas, refinery tail gas, pyrolysis gas and synthesis gas(ii) a In addition, methane tanks, manure and garbage fermentation tanks; and a large amount of gas is released in environments such as a papermaking pulp tank. These gases contain a large amount of hydrogen sulfide and CS 2 Organic sulfur such as COS, mercaptan, thioether and thiophene, and also contain a large amount of HCN and NH 3 . These gases, whether discharged directly into the atmosphere or indirectly after combustion, cause serious environmental pollution, such as the formation of odor, acid rain and haze, which are diffused in the air, and the synergistic effect of these toxic gases causes cancers, respiratory diseases and skin diseases, which directly endanger human health. If the gas is used as industrial raw material gas, the gas has great harm to industrial production, for example, serious corrosion of equipment and buildings is caused; in particular, the harm to industrial production of synthetic ammonia, organic synthesis and the like is more serious, for example, poisoning and deactivation of shift catalysts, synthetic ammonia catalysts, methanol catalysts, polymerization and cracking catalysts and the like are caused, copper consumption of a copper washing process of the synthetic ammonia is rapidly increased, the quality of products is reduced, the products are blackened and the like, wherein hydrogen sulfide is called cancer cells in the synthetic ammonia industry. Therefore, the development and research of desulfurization technology is becoming urgent and important.
The existing desulfurization technologies such as Claus process, alcohol amine process, MDEA process, G-V process, sulfolane process, A.D.A. process, hydroquinone process, vacuum carbonate process, tannin extract process, cobalt phthalocyanine process and the like mainly serve as primary desulfurization processes for removing hydrogen sulfide in industrial raw material gas but not CS in the gas 2 The desulfurization methods have low desulfurization efficiency, high cost, serious crystallization blockage and serious corrosion, and meanwhile, part of desulfurization solution is often discharged to control the content of secondary salt in the desulfurization solution to improve the desulfurization effect, thereby causing direct environmental pollution; meanwhile, the methods use a large amount of toxic chemical reagents, cause secondary pollution and have undesirable comprehensive effect.
In the early days, we have proposed "a method of buffering acetic acid, sodium acetate and ammonia in the form of ferrous hydroxide solution" [ see 1998 "journal of chemical industry", 49(1) ", P48-58]And a method for gas decarburization, desulfurization and decyanation by using an iron-alkali solution catalysis method (see Chinese patent ZL 99100596.1)]And the like, we generally refer to such a desulfurization method as a "ferric alkali solution desulfurization method" or a "complex iron desulfurization method" or a "chelate iron desulfurization method" by a gas desulfurization method of absorbing hydrogen sulfide in a gas with an aqueous solution containing iron ions or complex iron and then oxidizing the absorbed hydrogen sulfide to elemental sulfur with air. In the actual operation process, the 'ferric alkali solution desulfurization method' or 'complex iron desulfurization method' or 'chelate iron desulfurization method' has high hydrogen sulfide removal efficiency, but the ferric alkali solution has poor stability, complex iron is easy to degrade, and a large amount of ferrous sulfide precipitates can be generated particularly after the complex iron is contacted with hydrogen sulfide, so that the iron ion content in the solution is rapidly reduced, the desulfurization effect is rapidly reduced, equipment such as a desulfurization tower is seriously blocked, and the method is not suitable for gas desulfurization with high sulfur content. Meanwhile, the generated ferrous sulfide and the regenerated sulfur are mixed, and the mixture is like an earth explosive, and in the practical application process, the phenomena of spontaneous combustion and explosion occur. A great deal of practical demonstration shows that among all known iron compounds, EDTA-Fe (ethylene diamine tetraacetic acid), NTA-Fe (ferric nitrilotriacetate) and the like with the highest stability can generate a great deal of ferrous sulfide precipitation to cause spontaneous combustion and explosion. In addition, because iron ions in the complexing iron are lost in the operation process, complexing ligands such as EDTA and NTA can form a large amount of salt crystals to cause crystallization blockage of equipment; meanwhile, the complex ligands can be slowly degraded into smaller organic acid salts and amine salts, and the organic acid salts and the amine salts are converted into strong surfactants, so that a large amount of virtual bubbles and flying bubbles are caused, the production is seriously influenced, and the production cannot be continued. It is thus seen that the "iron-base solution" (complexed iron) desulfurization process has significant limitations and presents serious safety hazards. Therefore, for safety reasons, we have not widely spread the application of "ferric-alkali solution" (i.e. complex iron solution) desulfurization technology. In 1887, the Russian scientist Sergei Winogradsky discovered that beggaratoa (Beggiatoa) utilized hydrogen sulfide (H) 2 S) as an energy source, CO 2 As a mechanism of metabolism of the carbon source. After about 100 years, in 1984-1985, the research of oxidizing the sulfide in the wastewater by colorless sulfur oxidizing bacteria and oxygen in the dark environment by Cees Buisman of the Netherlands is successful, and the sulfur is realizedThe purpose of recovery, but its research is only focused on how to obtain extracellular elemental sulphur. Later, the research mainly focuses on the application and research field of sewage deodorization, the ThiOPAQ technology is developed, in 1992, the ThiOPAQ technology is utilized by the ThiOPAQ technology to remove hydrogen sulfide in methane, in 2002, the application in the field of natural gas desulfurization is realized in Canada, however, the technology generates a large amount of salt-containing wastewater in the practical application of natural gas desulfurization in China, the salt content in the desulfurization liquid is increased, and the desulfurization efficiency is obviously reduced, so the technology is not widely popularized and applied in China.
Since 1995, our research team has been working on the field of gas biological desulfurization, and screened a sulfur-philic oxygen-consuming heat-resistant alkali-tolerant bacterium named "GDJ-3" from soil in a salt lake of inner Mongolia, which has better homology with Alpha proteobacterium sp (97%) and Ochrobactrum sp (98%). The strain has good desulfurization effect and can be widely applied to the field of desulfurization of semi-water gas and shift gas for synthesizing ammonia in China. For this reason, we developed "biochemical iron-alkali solution catalytic gas desulfurization method", and applied for and granted a national patent on 09.09.2002, and then we made a more detailed study on GDJ-3.
Since then, the research of biological desulfurization in China is getting more and more hot, but the research is a theoretical research staying in a laboratory, and large-scale industrial application is not obtained. For example, the horse of south China university initially discusses the desulfurization mechanism of DS-3 strain (Rhodococcus erythropolis), and confirms that the strain has 64.08% and 85.86% of final desulfurization rates on 08 diesel oil and refined diesel oil, respectively, and can remove Dibenzothiophene (DBT) and DBT derivatives, but has relatively poor ability to remove BT and BT derivatives. There are also a number of researchers using Rhodococcus erythropolis (Rhodococcus erythropolis), Thiobacillus ferrooxidans (Thiobacillus ferrooxidans), Thiobacillus thiooxidans (Thiobacillus thiooxidans), Gordona sp, Pseudomonas sp, Arthrobacter sp, Dethiovibrio desulfurizati (Desulfuricans), Corynebacterium sp, Brevibacterium sp, Nocardia sp, and Bacillus polymyxa, respectivelyThe research of removing DBT and DBT derivatives in petroleum and ore is carried out by the strains of (Paenibacillus polyyxa), Mycobacterium phlei (Mycobacterium phlei GTIS10), Paenibacillus (Paenibacillus sp.) A11-2, Sulfolobus acidocaldarius, (Bririeytsp.), bacillus and the like, but the large-scale application and the effect of removing hydrogen sulfide and organic sulfur in gas are not realized. Some researchers have described the use of Thiobacillus ferrooxidans/Acidithiobacillus ferrooxidans and Thiobacillus denitrificans for the removal of H from natural gas 2 S, converted to elemental sulfur. Some researchers have also reviewed the use of Thiobacillus thioparus species (Thiobacillus thioparus) for H removal from gases 2 S, forming simple substance sulfur, thiosulfate, polythionate, sulfite, sulfate and other intermediate products. Still other investigators have reviewed the use of Thiobacillus thiooxidans (Thiobacillus thiooxidans) for the removal of H from gases 2 S, forming intermediate products such as elemental sulfur, thiosulfate, sulfate and the like. Some researchers reviewed the removal of H from gas with Xanthomonas (Xanthomonas sp.) 2 S, oxidizing into intermediate products such as elemental sulfur, thiosulfate, sulfate and the like. Some researchers have also reviewed the removal of H from gases with Pseudomonas acidovorans 2 S, forming intermediate products such as elemental sulfur, thiosulfate, sulfate and the like. Some researchers have also reviewed the use of Pseudomonas putida (Pseudomonas putida) for H removal from gases 2 S, forming intermediate products such as elemental sulfur, thiosulfate, sulfate and the like. Some researchers have also reviewed H removal from gases with Chlorella (Chlorobium limicola) 2 S, forming intermediate products such as elemental sulfur, thiosulfate, sulfate and the like. Some researchers have also reviewed the use of Thiospira fructicola (Thiomicrospira frisia) species for H removal from gases 2 S, in addition to being oxidized into elemental sulfur, intermediate products such as thiosulfate, sulfate and the like can also be generated. Some researchers have also reviewed the use of sulfur micro-spira sp for H removal from gases 2 S, besides being oxidized into elemental sulfur, intermediate products such as thiosulfate and sulfate can be generated. Some researchers have reviewed the use of snow whiteRemoving H in gas by thiobacillus (Thiothrix nivea) strain 2 S, besides being oxidized into elemental sulfur, intermediate products such as thiosulfate and sulfate can be generated. Some researchers have also reviewed the removal of H from gases by bacteria such as Microbacterium filamentosum (Hypericum sp.), Chlorophorbide (Chlorobium thiothium), Phlebopus estuarius (Prosthecochloris aestivii), Rhodospirillum halodura (Halorospira abdelmalemii), Microbacterium sulforaphicum (Thiobacillus cyclicum), Thiobacillus neapolis (Thiobacillus neapolis), Thiobacillus neoformans (Thiobacillus novalvus), Thiobacillus albugineus (Thiobacillus albertuss), Thiobacillus amethyoburni (Thiobacillus albertuss), Thiobacillus metabolically deficient Thiobacillus (Thiobacillus permotabolis), and the like 2 S, forming intermediate products such as thiosulfate, sulfate and the like besides elemental sulfur. Some researchers have reviewed the removal of H from gases by bacteria such as Thermoascus (Thermothermix azorensis), Microaerobe spirillum (Thioallispira microaerophila), Thiobacillus novelulus, Arthrobacter oxydans, and the like 2 S, forming intermediate products such as elemental sulfur, thiosulfate, sulfate and the like. Some researchers have reviewed the removal of H from gases by bacteria such as Agrobacterium sp, Bacillus sp, and the like 2 S, forming intermediate products such as elemental sulfur, thiosulfate, sulfate and the like. Some researchers have also reviewed the use of Paracoccus polyfunctionalus (Paracoccus versutus) for H removal from gases 2 S, forming intermediate products such as elemental sulfur, thiosulfate, sulfate and the like. Some researchers have reviewed the removal of H from gases by Chromobacterium (Chromobacterium), Achromobacter (Achromobacter), Desulfuromonas (Desulfuromonas), Mycobacterium (Mycobacterium), Arthrobacter (Arthrobacter), Flavobacterium (Flavobacterium), Xanthobacter (Xanthobacter), and the like 2 S, forming intermediate products such as elemental sulfur, thiosulfate, sulfate and the like. Some researchers have also reviewed the use of Thiobacillus thioparus (Thiobacillus thiopams) and Thiolalkalivibrio (Thiolalkalivibrio) for H removal from gases 2 S, forming intermediate products such as elemental sulfur, thiosulfate, sulfate and the like. The common feature of these bacterial desulfations is the "oxidative conversion of hydrogen sulfide to elemental sulfur, with the coproduction of thiosulfate, sulfite and sulfate". What is neededThus, when desulfurization is performed using these bacteria, the desulfurization efficiency gradually decreases as the concentration of by-products such as sulfate, thiosulfate, polythionate, and sulfite in the desulfurization solution gradually increases, and when the concentration thereof reaches a saturated state, crystallization of sulfate and the like occurs, which causes clogging of the apparatus.
Disclosure of Invention
In view of one or more of the problems with the prior art, the present invention provides the use of Campylobacter xanthus in desulfurization. Specifically, hydrogen sulfide and/or organic sulfur in sulfur-containing gas are absorbed by biological desulfurization liquid containing halofilm campylobacter xanthum; the biological desulfurization solution absorbing the hydrogen sulfide and/or organic sulfur is oxidized and regenerated by air/oxygen, sulfur is by-produced, and the regenerated biological desulfurization solution is recycled.
The invention provides an application of Campylobacter flavus in desulfurization of gas containing hydrogen sulfide and/or organic sulfur.
Preferably, the sulfur is hydrogen sulfide and/or organic sulfur in the sulfur-containing gas.
Preferably, the sulfur-containing gas is natural gas, coke oven gas, oil field gas, water gas, blast furnace gas, city gas, synthetic ammonia semi-water gas and shift gas, synthetic waste gas of dye factories, waste gas of chemical fiber factories or biogas; and/or
The total sulfur content in the sulfur-containing gas is less than 99.9% by volume.
When the Campylobacter flavus inhabitation salt film is used for desulfurization, no special requirement is made on the total sulfur content in the sulfur-containing gas before desulfurization, but in order to achieve better desulfurization effect, the total sulfide content in the sulfur-containing gas is preferably less than 99.9% (volume ratio).
Preferably, directly adding the bacteria liquid of the campylobacter flavus to the desulfurization liquid to prepare a biological desulfurization liquid, and performing desulfurization; or directly adding spores of Campylobacter flavus into the desulfurization solution, and gradually growing the spores into vegetative cells in the desulfurization process to perform desulfurization.
Preferably, the concentration of the bacteria liquid of the Campylobacter flavus in the desulfurization liquid is1 × 10 2 ~1×10 19 Per ml, preferably at a concentration of 1X 10 6 ~1×10 10 One per ml.
The pH value of the biological desulfurization solution is 2-12, and preferably, the pH value is not less than 7 and not more than 9.
The invention does not limit the concentration of the desulfurization bacteria in the biological desulfurization solution, but the optimal concentration of the desulfurization bacteria in the biological desulfurization solution is1 x 10 6 ~1×10 10 Per ml; the pH value of the biological desulfurization solution is not particularly required, but is optimally kept within the range of 7-9 in order to prevent acid-base corrosion of equipment.
Preferably, the desulfurization is carried out by absorption under normal pressure; and when the absorption is carried out under the normal pressure, the absorption temperature is 0-80 ℃.
More preferably, the absorption temperature is 15 to 25 ℃ during the absorption under normal pressure.
Preferably, after desulfurization, air/oxygen is introduced into the bacteria liquid of the Campylobacter flavus to regenerate the Campylobacter flavus, and sulfur is by-produced.
Preferably, the regeneration is carried out under normal pressure to regenerate the Campylobacter flavus; and when the regeneration is carried out under the normal pressure, the regeneration temperature is 0-100 ℃.
More preferably, the regeneration temperature is 25 to 40 ℃ during regeneration under normal pressure.
When the campylobacter flavus inhabitation membrane is used for desulfurization, the process conditions are not strictly limited, and the process conditions can be normal pressure absorption, negative pressure absorption or pressurized absorption, but the normal pressure absorption is preferably adopted; when the regeneration is carried out at normal pressure, the absorption temperature is 0-80 ℃, and the regeneration temperature is 0-100 ℃.
The previous researches show that in the campylobacter flavus desulfurization method, the bacteria can directly swallow sulfur-containing compounds into the bacteria, and then carry out aerobic digestion to convert the sulfur-containing compounds into elemental sulfur; the sulfur-containing compound may be hydrogen sulfide (H) 2 S), carbon disulfide (CS) 2 ) And sulfur-oxidized carbon (carbonyl sulfide COS), mercaptans (R-SH), thioethers (R-S-R'), and the like, which are volatile organic sulfur compounds. For convenience of presentation, we indicate as "< desulfurizing bacteria", so that the basic principle of the present invention is roughly summarized as follows:
when the gas contacts with the biological desulfurization solution, the following absorption reaction occurs:
⊙+H 2 S→⊙-H 2 S
⊙+COS→⊙-COS
⊙+CS 2 →⊙-CS 2
⊙+R-SH→⊙-R-SH
⊙+R-S-R’→⊙-R-S-R’
the sulfide-absorbed biological desulfurization solution is hereinafter referred to as "rich solution". The 'rich solution' is oxidized and regenerated by air under the action of the desulfurization bacteria, and the following regeneration reaction can occur:
⊙-H 2 S+1/2O 2 →S+H 2 O+⊙
⊙-COS+1/2O 2 →CO 2 +S+⊙
⊙-CS 2 +O 2 →CO 2 +2S+⊙
⊙-R-SH+1/2O 2 →R-OH+S+⊙
⊙-R-S-R’+1/2O 2 →R-O-R’+S+⊙
the rich solution after air oxidation is regenerated and converted into lean solution (i.e. biological desulfurization solution from which sulfide is removed), and the lean solution is recycled.
The main purpose of the invention is mainly the practicability of removing the sulfur-containing compounds in the gas, so the invention is directly applied to the actual production device, and the biological desulfurization solution can be recycled as long as the biological desulfurization solution is safe and stable and has high desulfurization efficiency; therefore, the detailed mechanism of the absorption reaction and regeneration reaction of bacterial desulfurization has not been studied in depth.
In order to realize the desulfurization process, the inventor of the application carries out direct production test on the existing desulfurization device in the desulfurization process of the coke oven gas of the special material Co. There are two types of coke oven gas desulfurization processes by holy taifu special materials limited: the first is normal pressure absorption, high tower regeneration flow (referred to as "high tower regeneration flow" for short); the second is a normal pressure absorption, jet absorption air regeneration process (referred to as "one tower process" for short).
The first is normal pressure absorption, high tower regeneration flow: directly adding desulfurization bacteria into desulfurization solution in two sets of desulfurization devices of high tower regeneration process of ammonia desulfurization to control bacterial concentration to be 1 x 10 6 ~1×10 10 And (4) performing desulfurization test.
The second is a normal pressure absorption and jet absorption air regeneration process: directly adding desulfurization bacteria into desulfurization solution in a set of desulfurization devices of a tower-type process of the existing ammonia method desulfurization to control the bacteria concentration to be 1 x 10 6 ~1×10 10 And (4) performing desulfurization test.
The campylobacter xanthus with salt-depositing membranes has wide industrial application in the field of sulfur-containing gas desulfurization, can be used for desulfurization of natural gas, coke oven gas, oil field gas, water gas, blast furnace gas, city gas, synthetic ammonia semi-water gas and conversion gas, synthetic waste gas of dye factories, waste gas of chemical fiber factories, biogas and other industrial raw gas or waste gas containing hydrogen sulfide and organic sulfur, and the total sulfur content in the sulfur-containing gas is less than 99.9 percent (volume ratio). Not only can remove hydrogen sulfide in the organic sulfur, but also has certain removal capacity for organic sulfur. And the traditional wet desulphurization method can not keep high desulphurization efficiency economically for a long time, but the desulphurization method can keep high desulphurization efficiency economically for a long time because the halophilic membrane campylobacter flavus can be regenerated and used.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of a laboratory desulfurization screening test apparatus.
FIG. 2 is a schematic diagram of an atmospheric absorption, high tower regeneration scheme in accordance with a first embodiment.
FIG. 3 is a schematic diagram of a regeneration process of the air of the atmospheric absorption and the jet absorption according to the second embodiment.
Detailed Description
A method of desulfurizing Campylobacter flavus of the present invention is described below with reference to specific embodiments for better illustrating the present invention and should not be construed as limiting the claims of the present invention.
The strain Flavellex salsolisticola used in the present invention was purchased from Ningbo Ming boat Biotech Co.
According to the information on the above-mentioned purchased strains provided by Ningbomin Biotechnology Ltd: the strain has the scientific name of Flaviflex salsibostriata and belongs to the phylum Actinobacillae/class Actinobacteriales/family Actinomycetales/family Campylobacter yellow. And written in the purchase information is "Other names: KCTC 33148 ".
In addition, my sequenced 16S rRNA on this strain after purchase, with the following results: GTGGATTAGTGGCGAACGGGTGAGTAACACGTGAGTAACCTGCCCCTTTCTTCGGGATAAGCTTGGGAAACTGGGTCTAATACCGGATATTCAGCGGCTGCCGCATGGTGGTTGTTGGAAAGATTTATTGGGAGGGGATGGGCTCGCGGCCTATCAGCTTGTTGGTGGGGTGATGGCCTACCAAGGCGTCGACGGGTAGCCGGCCTGAGAGGGTGACCGGCCACACTGGGACTGAGATACGGCCCAGACTCCTACGGGAGGCAGCAGTGGGGAATATTGCACAATGAGCGAAAGCTTGATGCAGCGACGCCGCGTGAGGGATGACGGCTTTCGGGTTGTAAACCTCTTTCGGCAGGGAACAAGTCCAGGTTTTGGCCTGGTTGAGGGTACCTGCATAAGAAGCGCCGGCTAACTACGTGCCAGCAGCCGCGGTAATACGTAGGGCGCGAGCGTTGTCCGGAATTATTGGGCGTAAAGAGCTCGTAGGCGGCTTGTCGCGTCTGCTGTGAAAACGCGGGGCTTAACTCCGCGCTTGCAGTGGGTACGGGCAGGCTTGAGTGTAGTAGGGGAGACTGGAATTCCTGGTGTAGCGGTGGAATGCGCAGATATCAGGAGGAACACCGATGGCGAAGGCAGGTCTCTGGGCTATAACTGACGCTGAGGAGCGAAAGCATGGGGAGCGAACAGGATTAGATACCCTGGTAGTCCATGCCGTAAACGTTGGGCACTAGGTGTGGGGGTTTTTGACTTCTGCGCCGTAGCTAACGCATTAAGTGCCCCGCCTGGGGAGTACGGCCGCAAGGCTAAAACTCAAAGGAATTGACGGGGGCCCGCACAAGCGGCGGAGCATGCGGATTAATTCGATGCAACGCGAAGAACCTTACCAAGGCTTGACATACACTGCGATGTTCCAGAGATGGGGCAGCCTTCGGGGTGGTGTACAGGTGGTGCATGGTTGTCGTCAGCTCGTGTCGTGAGATGTTGGGTTAAGTCCCGCAACGAGCGCAACCCTTGTCTCGTGTTGCCAGCACATGATGGTGGGGACTCACGAGAGACTGCCGGGGTTAACTCGGAGGAAGGTGGGGATGACGTCAAATCATCATGCCCCTTATGTCTTGGGCTTCACGCATGCTACAATGGCCGGTACAGAGGGTTGCGATGTCGTAAGGCTGAGCGAATCCCTTAAAGCCGGTCTCAGTTCGGATTGGGGTCTGCAACTCGACCCCATGAAGTCGGAGTCGCTAGTAATCGCAGATCAGCAACGCTGCGGTGAATACGTTCCCGGGCCTTGTACACACCGCCCGTCACGTCACGAAAGTTGG
Compared with the gene sequence of the strain KCTC 33148, the similarity is 99.92 percent. Therefore, the Chinese name of the purchased strain should be Campylobacter salsibioticola (Flavellex sarstriicola). Hereinafter, the description will be made with "Campylobacter xanthus (Flaviflexus salsibiriiostataria)".
Example 1
The enlarged culture method of the campylobacter juncea is as follows:
the glycerol-preserved strain was recovered and cultured in an incubator with a solid medium at 28 ℃ for 24 hours. Scraping off the whole flora of Campylobacter flavidus (Flavelexus salsiospatialia) on the cultured solid culture medium, pouring into a triangular flask filled with 120ml liquid culture medium, dispersing, and shaking uniformly to obtain the enrichment culture mother liquor. Adding 5ml of fresh enrichment culture mother liquor into 24 triangular flasks respectively filled with 120ml of liquid culture medium, wrapping triangular flask mouths, putting into a bacteria culture shaking table, and culturing at 28 ℃ and 150r/min for 3-5 days to obtain the enrichment culture liquor. The proliferating bacteria liquid can be directly used for industrial production.
Liquid medium composition (g/L): 5.0 parts of peptone, 1.0 part of yeast powder, 0.1 part of ferric citrate, 19.45 parts of sodium chloride, 5.98 parts of magnesium chloride, 3.24 parts of sodium sulfate, 1.8 parts of calcium chloride, 0.55 part of potassium chloride, 0.16 part of sodium carbonate, 0.08 part of potassium bromide, 0.034 part of strontium chloride, 0.022 part of boric acid, 0.004 part of sodium silicate, 0.0024 part of sodium fluoride, 0.0016 part of sodium nitrate and 0.008 part of disodium hydrogen phosphate, wherein the pH value is 7.6 +/-0.2 and 28 ℃.
The solid medium is simply a liquid medium to which an appropriate agar is added.
The applicant first carried out a laboratory desulfurization test on a campylobacter flaviflex salstrioticola bacterial solution (a proliferated bacterial solution obtained by the above culture) of the halophilic membrane yellow.
The laboratory desulfurization test apparatus is shown in FIG. 1.
FIG. 1 is a schematic diagram of a laboratory desulfurization test apparatus. Wherein, 1 is an absorption bottle, 2 is a bacterium liquid, 3 is a gas inlet, and 4 is a gas outlet.
Referring to fig. 1, the operating method for the laboratory desulfurization screening test was: about 150ml of Campylobacter flavus strain liquid 2 (prepared at a strain concentration of 10) 6 ~10 7 One/ml) is filled into a 250ml glass absorption bottle 1, gas containing hydrogen sulfide (the concentration of hydrogen sulfide in nitrogen is about 10000ppm (volume ratio) and the flow is controlled at 80ml/min) is introduced from a gas inlet 3 and enters the absorption bottle 1, and the hydrogen sulfide is absorbed by a bacterial liquid 2 after passing through a bacterial liquid 2 layer; and (3) the gas from which the hydrogen sulfide is removed flows out from the gas outlet 4, and enters an absorption bottle filled with blue iodine-containing starch solution, if the blue iodine-containing starch solution is colorless, the bacteria liquid 2 absorbs the hydrogen sulfide to be saturated, the absorption is stopped, and the absorption time t (min) is recorded. Then, the bacterial liquid 2 saturated by absorbing the hydrogen sulfide is regenerated, and the regeneration step is as follows: air (the flow rate is controlled to be about 200 ml/min) is introduced into the absorption bottle 1 from the gas inlet 3, and hydrogen sulfide in the bacterial liquid 2 is metabolized into elemental sulfur by bacteria after passing through the bacterial liquid 2 layer absorbing the hydrogen sulfide; after regeneration, the gas flows out from the gas outlet 4, is emptied and is regenerated for 30 min. The regenerated bacteria liquid 2 is used for absorbing hydrogen sulfide after elemental sulfur is removed: still repeating the above absorbing step; then, repeating the above regeneration steps, thus, absorbing and regenerating; and (3) absorbing and regenerating again, and then recording the saturation time t of absorption, the pH value before absorption (or the pH value after regeneration) and the pH value after absorption of each time. First, we carried out a reference experiment using 150ml of sodium carbonate solution having a concentration of 3g/L in the above manner, and the results of the experiment on the absorption of hydrogen sulfide by the reference solution are shown in Table 1. Then, the Campylobacter flavus bacterium composition solution 2 of the present invention (the bacterium concentration was adjusted to 10) was added to 150ml of 3% sodium carbonate solution 6 ~10 7 Piece/ml), the above experiments were repeated, and the experimental results of the absorption of hydrogen sulfide by the campylobacter flavus bacterial liquid of the present invention are shown in table 2. (note in particular that the newly prepared 3% sodium carbonate solution has a high pH value and is unstable, so that the absorption time is long just before the start of the preparation, so that the previous unstable data are not needed, and only the experimental data after the pH value is slightly stable are adopted, the experimental temperature of the experiment is 35 ℃).
TABLE 1 150ml of carbonic acid at a concentration of 3g/LSodium solution, H in gas 2 The S concentration is 9995ppm (volume ratio), the flow is 80ml/min, the normal pressure is normal pressure, 35 ℃, the absorption saturation experiment result is obtained
Figure BDA0003686446330000091
Figure BDA0003686446330000101
TABLE 2 desulfurization solution (total bacterial concentration of 10) composed of Campylobacter xanthus (Flavellex salstricosta) added to 150ml sodium carbonate solution with 3g/L concentration 6 ~10 7 One/ml), H in gas 2 The S concentration is 9995ppm (volume ratio), and the flow rate is 80ml/min
The experimental result of absorption saturation at normal pressure and 35 DEG C
Figure BDA0003686446330000102
Figure BDA0003686446330000111
As can be seen from the data in tables 1 and 2, the desulfurization solution containing Campylobacter flavus (Flavellex salstriostrea) has good desulfurization ability and has good ability to continue desulfurization after regeneration and recovery.
In order to reduce the test workload and ensure the real and effective test result, the production experiment of desulfurization is carried out by directly using the flaviviruses salina bacteria liquid (the proliferated bacteria liquid obtained above) on the coke oven gas desulfurization process device of the Toyota-rich special material company Limited. The enterprise has two desulfurization processes: the first is normal pressure absorption, high tower regeneration flow (referred to as "high tower regeneration flow" for short); the second is a normal pressure absorption, jet absorption air regeneration process (referred to as a tower process for short); the actual process flow is as follows: two sets of identical high tower regeneration processes are connected in parallel for desulfurization (generally called 'primary desulfurization'), then coke oven gas after being connected in parallel for desulfurization is mixed together, and then the mixed gas enters a desulfurization device of a tower type tower process for further desulfurization (generally called 'secondary desulfurization').
Wherein, the first normal pressure absorption and high tower regeneration process: directly adding halofilm yellow campylobacter into the desulfurization liquid in two sets of desulfurization devices in the high tower regeneration process of the existing ammonia method desulfurization, and controlling the bacterial concentration to be 1 x 10 8 And (4) obtaining a biological desulfurization solution for desulfurization test.
The second normal pressure absorption and jet absorption air regeneration process: directly adding halomembrane yellow campylobacter into the desulfurizing liquid in a set of desulfurizing device of tower-type process of ammonia desulfurization to control its bacterial concentration at 1X 10 8 And (4) obtaining biological desulfurization solution for desulfurization test.
Embodiment one ("high tower regeneration scheme") is shown in figure 2.
FIG. 2 is a schematic diagram of an atmospheric absorption, high tower regeneration scheme according to the first embodiment. Wherein, 1 is coke oven gas before desulfurization, 2 is a desulfurizing tower, 3 is desulfurized coke oven gas, 4 is barren liquor, 5 is rich liquor, 6 is a desulfurizing liquor circulating tank, 7 is a desulfurizing pump, 8 is a high tower regeneration tower, 9 is air, 10 is an air compressor, 11 is sulfur foam, 12 is vent gas, 13 is a sulfur foam tank, 14 is a sulfur foam pump, 15 is a filter, 16 is sulfur paste, 17 is filtrate, 18 is a filtrate tank, and 19 is a filtrate pump.
Among them, the biological desulfurization solution in which the sulfide is absorbed is called "rich solution".
The rich solution after air oxidation is regenerated and converted into lean solution, and the lean solution is recycled.
Referring to fig. 2, coke oven gas 1 enters from the bottom of a desulfurizing tower 2 before desulfurization and is in countercurrent contact with barren liquor 4 sprayed from the top; sulfur-containing compounds in the coke oven gas 1 before desulfurization are absorbed by the barren solution 4, and the coke oven gas 1 before desulfurization is converted into desulfurized coke oven gas 3 (called as 'coke oven gas after primary desulfurization') which flows out from the top of the desulfurizing tower 2; the lean solution 4 having absorbed the sulfur-containing compounds is converted into a rich solution 5 at the bottom of the desulfurization tower 2; the rich liquid 5 flows out from the bottom of the desulfurizing tower 2, enters a desulfurizing liquid circulation tank 6, is sent into a high tower regeneration tower 8 from the bottom by a desulfurizing pump 7, air 9 is pressurized by an air compressor 10 and then also enters the high tower regeneration tower 8 from the bottom, in the high tower regeneration tower 8, the rich liquid 5 and the air 9 are fully mixed, sulfur-containing compounds in the rich liquid 5 are metabolized into elemental sulfur by bacteria by using oxygen to form sulfur foam 11, the sulfur foam 11 is floated to the top of the high tower regeneration tower 8 and then automatically overflows to a sulfur foam tank 13, and then is sent to a filter 15 by a sulfur foam pump 14 for filtering to obtain sulfur paste 16 and filtrate 17, the sulfur paste 16 can be sold as a byproduct, and the filtrate 17 enters a filtrate tank 18 and then is sent to the desulfurizing liquid circulation tank 6 by a filtrate pump 19 for recycling; the air 9 is changed into vent gas 12 after reacting in the high tower regeneration tower 8 and is released to the outside; after the air 9 is metabolized and regenerated by bacteria in the high tower regeneration tower 8, the rich liquor 5 is converted into the lean liquor 4, and the lean liquor 4 automatically flows into the desulfurizing tower 2 for recycling.
In the first embodiment, a coke oven gas desulfurization test is performed on two sets of parallel high tower regeneration primary desulfurization system devices of a coke oven gas desulfurization system of the special material of holy taifu company, the implementation flow is shown in fig. 2, and the equipment specifications and parameters are shown in table 3.
Wherein, the temperature in normal pressure absorption is 35 ℃, and the regeneration temperature in normal pressure regeneration is 40 ℃.
Table 3 specifications of each apparatus in the first embodiment
Device Specification (mm) Number of Remarks for note
Desulfurizing tower (2)) DN7000×32300 2 (parallel)
High tower regenerative tower (8) DN5000×47000 2
Doctor solution circulation tank (6) DN4600L=12440 2
Desulphurization pump (7) Q=2500m 3 /h,H=60 3 Two switches on and one switch off
Air compressor (10) DN5000×5400 1
Sulfur foam groove (13) DN3400,H=6030 2
Sulfur foam pump (14) Q=30m 3 /h,H=50 2 One for one and one for one
Filter (15) Filter area 150 square meter 2
Filtrate tank (18) DN2800×2125 1
Filtrate pump (19) Q=30m 3 /h,H=35m 2 Open one and prepare one
Before 12 months in 2018, the enterprise carries out desulfurization by using a desulfurization method (hereinafter, referred to as a 'PDS' method for short, the desulfurization method is a method for removing hydrogen sulfide widely used in industrial production in China) by using cobalt phthalocyanine as a catalyst, and the operation conditions of a tower No. 1 and a tower No. 2 are shown in tables 5 and 6. After 12 months in 2018, the enterprise adds the campylobacter xanthus of the invention into the desulfurization solution of the existing desulfurization process, and the enterprise desulfurizes by using the campylobacter xanthus of the invention (hereinafter, referred to as "DDS" method), and the operation conditions of the tower # 1 and the tower # 2 in 2019, 2020 and 2021 are shown in tables 8 and 9, tables 11 and 12, tables 14 and 15. From the operating point of view, the desulfurization efficiency of the DDS is higher than that of the PDS under the same conditions.
The second embodiment ("one-column flow scheme") is shown in FIG. 3.
FIG. 3 is a schematic diagram of a regeneration process of the air of the atmospheric absorption and the jet absorption according to the second embodiment. Wherein 3 is coke oven gas after primary desulfurization, 20 is a tower-type desulfurization tower, 21 is coke oven gas after tower-type desulfurization, 22 is a tower-type regeneration tank, 23 is tower-type barren liquor, 24 is tower-type pregnant solution, 25 is a desulfurization regeneration pump, 26 is an air injection absorber, 27 is air, 28 is vent gas, 29 is sulfur foam, 30 is a sulfur foam tank, 31 is a sulfur foam pump, 32 is a filter, 33 is filtrate, 34 is sulfur paste, 35 is a filtrate tank, and 36 is a filtrate pump.
Referring to fig. 3, the coke oven gas 3 after the first-stage desulfurization enters from the bottom of a tower-type desulfurization tower 20 and is in countercurrent contact with a tower-type barren solution 23 sprayed from the top; sulfur-containing compounds in the coke oven gas 3 after the primary desulfurization are absorbed by a tower-type barren liquor 23, and the coke oven gas 3 after the primary desulfurization is converted into tower-type desulfurized coke oven gas 21 to flow out from a gas outlet of a tower-type desulfurizing tower 20; a tower-type lean solution 23 having absorbed sulfur-containing compounds is converted into a tower-type rich solution 24 at the bottom of a tower-type desulfurizing tower 20; a tower-type rich liquid 24 is pumped from the bottom of a tower-type desulfurization tower 20 by a desulfurization regeneration pump 25, enters an air injection absorber 26 after being pressurized, and absorbs air 27; a tower-type rich liquid 24 and air 27 are fully and uniformly mixed in an air jet absorber 26, and then enter the regeneration tank 22 from the bottom through a tail pipe of the air jet absorber 26; in the regeneration tank 22, a tower-type rich solution 24 and air 27 are fully mixed, sulfur-containing compounds in the tower-type rich solution 24 are metabolized into elemental sulfur by bacteria to form sulfur foam 29, then the sulfur foam automatically overflows to a sulfur foam tank 30, and the sulfur foam is sent to a filter 32 by a sulfur foam pump 31 to be filtered, so that sulfur paste 34 and filtrate 33 are obtained through filtration; the sulfur paste 34 may be sold as a by-product; the filtrate 33 enters a filtrate tank 35 and is sent to a tower-type desulfurizing tower 20 by a filtrate pump 36 for recycling; the air 27 becomes the atmospheric air 28 to be released to the outside; after the air 27 is regenerated in the regeneration tank 22, a tower rich liquid 24 is converted into a tower lean liquid 23, and the tower lean liquid automatically flows into a tower desulfurization tower 20 from a desulfurization liquid inlet for recycling.
In the second embodiment, a coke oven gas desulfurization test is performed on a tower type secondary desulfurization system device of a coke oven gas desulfurization system of the special material of holy taifu company, the implementation flow is shown in fig. 3, and the equipment specifications and parameters are shown in table 4.
Wherein, the temperature in normal pressure absorption is 35 ℃, and the regeneration temperature in normal pressure regeneration is 40 ℃.
TABLE 4 specification of each apparatus in the second embodiment
Device Specification (mm) Number of Remarks to note
A tower type desulfurizing tower (20) DN9000×30000 1
A tower type regeneration tower (22) DN9000/10000,H=12900 1 At the top of a tower-type desulfurizing tower
Desulphurization pump (25) Q=2500m 3 /h,H=60 2 One for one and one for one
Ejector (26) 50m 3 /h 60 pieces of 30-50 long openings
Sulfur foam tank (30) DN3400,H=6030 1
Sulfur foam pump (31) Q=30m 3 /h,H=50 2 One for one and one for one
Filter (32) Filter area 150 square meter 1
Filtrate tank (35) DN2800×2125 1
Filtrate pump (36) Q=30m 3 /h,H=35m 2 One for one and one for one
Before 12 months in 2018, the enterprise carries out desulfurization by a desulfurization method (hereinafter referred to as a "PDS" method) by using cobalt phthalocyanine as a catalyst, and the operation condition of a desulfurization device of a tower process is shown in Table 7. After 12 months in 2018, the enterprise adds the campylobacter xanthus of the invention into the desulfurization solution of the existing desulfurization process (hereinafter, abbreviated as "DDS" method) for desulfurization, and the operation conditions of the desulfurization device of the tower process in 2019, 2020 and 2021 are shown in tables 10, 13 and 16. From the operating point of view, the desulfurization efficiency of DDS is far higher than that of PDS under the same conditions.
TABLE 52018 operating conditions of column # 1 using PDS
Figure BDA0003686446330000141
TABLE 62018 operating conditions of column # 2 using PDS
Figure BDA0003686446330000142
TABLE 72018 Single column PDS run conditions
Figure BDA0003686446330000143
TABLE 82019 operation of column # 1 using DDS
Figure BDA0003686446330000144
Figure BDA0003686446330000151
TABLE 92019 operation of 2# column with DDS
Figure BDA0003686446330000152
TABLE 102019 operation with one tower DDS
Figure BDA0003686446330000153
TABLE 112020 operation of 1# column with DDS
Figure BDA0003686446330000154
TABLE 122020 operation of 2# column with DDS
Figure BDA0003686446330000161
TABLE 132020 operation with one tower DDS
Figure BDA0003686446330000162
TABLE 142021 operation of 1# column with DDS
Figure BDA0003686446330000163
TABLE 152021 operation of 2# column with DDS
Figure BDA0003686446330000164
Figure BDA0003686446330000171
TABLE 162021 operation when DDS was used in one tower
Figure BDA0003686446330000172
(Note: data in tables 5 to 16, operational data due to production abnormality is removed).
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Sequence listing
<110> Beijing Boyuan Hengsheng technology Limited
TONGLING PACIFIC SPECIAL MATERIALS Co.,Ltd.
Beijing Hengtai Yuan Shenggao Tech Co Ltd
Jiangxi Yongfeng Boyuan Industrial Co.,Ltd.
Beijing hong Long environmental protection Limited company
<120> application of Campylobacter flavus with salt-inhabiting membrane in desulfurization
<160> 1
<170> SIPOSequenceListing 1.0
<210> 1
<211> 1322
<212> DNA
<213> Campylobacter flavidus (Flavellex salsolivacola)
<400> 1
gtggattagt ggcgaacggg tgagtaacac gtgagtaacc tgcccctttc ttcgggataa 60
gcttgggaaa ctgggtctaa taccggatat tcagcggctg ccgcatggtg gttgttggaa 120
agatttattg ggaggggatg ggctcgcggc ctatcagctt gttggtgggg tgatggccta 180
ccaaggcgtc gacgggtagc cggcctgaga gggtgaccgg ccacactggg actgagatac 240
ggcccagact cctacgggag gcagcagtgg ggaatattgc acaatgagcg aaagcttgat 300
gcagcgacgc cgcgtgaggg atgacggctt tcgggttgta aacctctttc ggcagggaac 360
aagtccaggt tttggcctgg ttgagggtac ctgcataaga agcgccggct aactacgtgc 420
cagcagccgc ggtaatacgt agggcgcgag cgttgtccgg aattattggg cgtaaagagc 480
tcgtaggcgg cttgtcgcgt ctgctgtgaa aacgcggggc ttaactccgc gcttgcagtg 540
ggtacgggca ggcttgagtg tagtagggga gactggaatt cctggtgtag cggtggaatg 600
cgcagatatc aggaggaaca ccgatggcga aggcaggtct ctgggctata actgacgctg 660
aggagcgaaa gcatggggag cgaacaggat tagataccct ggtagtccat gccgtaaacg 720
ttgggcacta ggtgtggggg tttttgactt ctgcgccgta gctaacgcat taagtgcccc 780
gcctggggag tacggccgca aggctaaaac tcaaaggaat tgacgggggc ccgcacaagc 840
ggcggagcat gcggattaat tcgatgcaac gcgaagaacc ttaccaaggc ttgacataca 900
ctgcgatgtt ccagagatgg ggcagccttc ggggtggtgt acaggtggtg catggttgtc 960
gtcagctcgt gtcgtgagat gttgggttaa gtcccgcaac gagcgcaacc cttgtctcgt 1020
gttgccagca catgatggtg gggactcacg agagactgcc ggggttaact cggaggaagg 1080
tggggatgac gtcaaatcat catgcccctt atgtcttggg cttcacgcat gctacaatgg 1140
ccggtacaga gggttgcgat gtcgtaaggc tgagcgaatc ccttaaagcc ggtctcagtt 1200
cggattgggg tctgcaactc gaccccatga agtcggagtc gctagtaatc gcagatcagc 1260
aacgctgcgg tgaatacgtt cccgggcctt gtacacaccg cccgtcacgt cacgaaagtt 1320
gg 1322

Claims (10)

1. Use of Campylobacter flavus in desulfurization of gases containing hydrogen sulfide and/or organic sulfur.
2. Use according to claim 1, characterized in that: the sulfur is hydrogen sulfide and/or organic sulfur in the sulfur-containing gas.
3. Use according to claim 2, characterized in that: the sulfur-containing gas is natural gas, coke oven gas, oil field gas, blast furnace gas, city gas, gas, water gas, synthetic ammonia semi-water gas, shift gas, synthetic waste gas of a dye plant, sewage gas of a chemical fiber plant or methane; and/or
The total sulfur content in the sulfur-containing gas is less than 99.9% by volume.
4. Use according to claims 1-3, characterized in that: directly adding the bacteria liquid of the campylobacter xanthum into the desulfurization liquid to prepare a biological desulfurization liquid for desulfurization; or directly adding spores of Campylobacter flavus into the desulfurization solution, and gradually growing the spores into vegetative cells in the desulfurization process to perform desulfurization.
5. Use according to claim 4, characterized in that: the concentration of the bacteria liquid of the Campylobacter flavus in the desulfurization liquid is1 multiplied by 10 2 ~1×10 19 One/ml, preferably at a concentration of 1X 10 6 ~1×10 10 Per ml; and/or
The pH value of the biological desulfurization solution is 2-12, and preferably, the pH value is not less than 7 and not more than 9.
6. Use according to claim 1, characterized in that: absorbing at normal pressure for desulfurization; and when the absorption is carried out under the normal pressure, the absorption temperature is 0-80 ℃.
7. Use according to claim 6, characterized in that: and when the absorption is carried out under normal pressure, the absorption temperature is 15-25 ℃.
8. Use according to any one of claims 1 to 7, characterized in that: and after desulfurization, introducing air/oxygen into the bacteria liquid of the Campylobacter halophila to regenerate the Campylobacter halophila, and by-producing sulfur.
9. Use according to claim 8, characterized in that: regeneration under normal pressure is selected for regeneration of the campylobacter xanthus; and when the regeneration is carried out under the normal pressure, the regeneration temperature is 0-100 ℃.
10. Use according to claim 9, characterized in that: and when the regeneration is carried out under the normal pressure, the regeneration temperature is 25-40 ℃.
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AU484475B2 (en) * 1972-03-27 1974-10-03 Scm Chemicals Limited An improved chemical process
EP0218958A2 (en) * 1985-10-15 1987-04-22 Combustion Engineering, Inc. Microbiological desulfurization of gases
CN105420139A (en) * 2015-05-25 2016-03-23 蒋建平 Halophilic desulfurized bacterial strain and application thereof
CN113667616A (en) * 2021-07-15 2021-11-19 长江大学 Iron reducing bacterium DH4 strain and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU484475B2 (en) * 1972-03-27 1974-10-03 Scm Chemicals Limited An improved chemical process
EP0218958A2 (en) * 1985-10-15 1987-04-22 Combustion Engineering, Inc. Microbiological desulfurization of gases
CN105420139A (en) * 2015-05-25 2016-03-23 蒋建平 Halophilic desulfurized bacterial strain and application thereof
CN113667616A (en) * 2021-07-15 2021-11-19 长江大学 Iron reducing bacterium DH4 strain and application thereof

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Title
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