CN116286443A - Salmonella and application thereof - Google Patents
Salmonella and application thereof Download PDFInfo
- Publication number
- CN116286443A CN116286443A CN202211092983.7A CN202211092983A CN116286443A CN 116286443 A CN116286443 A CN 116286443A CN 202211092983 A CN202211092983 A CN 202211092983A CN 116286443 A CN116286443 A CN 116286443A
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- China
- Prior art keywords
- halomonas
- gas
- time
- desulfurization
- sulfur
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Images
Classifications
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Abstract
The invention provides halomonas and corresponding preserved information of the halomonas, and also provides application of the halomonas in desulfurizing hydrogen sulfide and/or organic sulfur-containing gas. The method for desulfurizing halomonas provided by the invention can maintain high desulfurizing efficiency economically for a long time. The halomonas desulfurization method disclosed by the invention has wide industrial application, can be used for desulfurizing natural gas, and can also be used for desulfurizing coke oven gas, oilfield gas, blast furnace gas, urban gas, synthetic ammonia semi-water gas and shift gas, synthetic waste gas of a dye factory, blow-down gas of a chemical fiber factory, biogas, and other industrial raw material gas or waste gas containing hydrogen sulfide and organic sulfur, wherein the total sulfur content in the sulfur-containing gas is less than 99.9% (volume ratio).
Description
Technical Field
The invention belongs to the technical field of biological purification treatment of industrial feed gas and waste gas containing hydrogen sulfide and/or organic sulfur, and particularly relates to halomonas and application thereof.
Background
Due to the rapid development of society, the large-scale exploitation of natural gas, coal mine, oilfield gas and shale gas is driven; the widespread use of fossil fuels, such as coal and petroleum, has resulted in the production of large amounts of coke oven gas, water gas, synthetic ammonia semi-water gas and shift gas, refinery off gas, pyrolysis gas, and syngas; in addition, a methane tank, a fecal and garbage fermentation tank; and in the environment of papermaking pulp tanks, a great amount of gas is released. These gases contain a large amount of hydrogen sulfide and CS 2 Organic sulfur such as COS, thiol, thioether, and thiophene, and a large amount of HCN and NH 3 . These gases, whether directly vented to the atmosphere or indirectly vented to the atmosphere after combustion, can cause serious environmental pollution. If these gases are used as industrial raw material gases, the industrial production is extremely harmful, for example, serious corrosion of equipment and buildings is caused; especially, the method is more serious in hazard to industries such as synthetic ammonia, organic synthesis and the like, for example, poisoning and deactivation of a shift catalyst, a synthetic ammonia catalyst, a methanol catalyst, a polymerization catalyst, a cracking catalyst and the like are caused, copper loss of a copper washing process of the synthetic ammonia is also increased rapidly, product quality is reduced, and a product is blackened, wherein hydrogen sulfide is called as a cancer cell in the synthetic ammonia industry. Therefore, development and research of desulfurization technologies are becoming urgent and important.
The prior desulfurization technology such as Claus method, alcohol amine method, MDEA method, G-V method, sulfolane method, A.D.A. method, hydroquinone method, vacuum carbonate method, tannin extract method, phthalocyanocobalt method and the like is mainly used as a primary desulfurization method to remove hydrogen sulfide in industrial raw material gas, but not CS in the gas 2 Organic sulfur such as COS, mercaptan, thioether, thiophene, etc., and these desulfurization methods have low desulfurization efficiency, high cost, severe crystal blockage and severe corrosion, and at the same time, a part of desulfurization liquid is often discharged to reduce the content of secondary salt in the desulfurization liquid to improve the desulfurization effect, and these methods are used in large amountsToxic chemical reagents can also cause secondary pollution, and the comprehensive effect is not ideal.
In the early stage, we proposed a "buffer solution method of acetic acid, sodium acetate and ammonia of ferrous hydroxide" [ see 1998 journal of chemical engineering, 49 (1), P48-58 ]]"gas decarbonization, desulfurization and decyanation method by iron-alkali solution catalysis" [ see Chinese patent ZL99100596.1 ]]And the like, by a gas desulfurization method in which hydrogen sulfide in a gas is absorbed by an aqueous solution containing iron ions or complex iron and then the absorbed hydrogen sulfide is oxidized to elemental sulfur with air, we generally call this desulfurization method "iron alkali solution desulfurization method" or "complex iron desulfurization method" or "chelate iron desulfurization method". In the actual operation process, we find that the efficiency of removing hydrogen sulfide by an iron alkali solution desulfurization method or a complex iron desulfurization method or a chelate iron desulfurization method is very high, however, the stability of the iron alkali solution is poor, complex iron is easy to degrade, and particularly, a large amount of ferrous sulfide precipitates can be generated after the iron alkali solution contacts with hydrogen sulfide, so that the content of iron ions in the solution is rapidly reduced, the desulfurization effect is rapidly reduced, and the phenomenon of serious blockage of equipment such as a desulfurizing tower is caused, so that the iron alkali solution is not suitable for gas desulfurization with high sulfur content. Meanwhile, the generated ferrous sulfide and regenerated sulfur are mixed to form a soil explosive, and in the practical application process, multiple spontaneous combustion and explosion phenomena occur. A large number of practical applications show that among all known iron compounds, even EDTA-Fe (ethylenediamine tetraacetic acid iron) or NTA-Fe (nitrilotriacetic acid iron) with the highest stability is used, a large amount of ferrous sulfide precipitates to cause spontaneous combustion and explosion phenomena. In addition, during the operation process, due to the loss of iron ions in the complex iron, a large amount of salt crystals can be formed by the complex ligands EDTA, NTA and the like, so that the crystallization blockage of equipment is caused; meanwhile, the complex ligands can be slowly degraded into organic acid salts and amine salts of smaller molecules, and are converted into strong surfactants, so that a large number of vacuoles and flying bubbles are caused, the production is seriously influenced, and the production cannot be continued. Therefore, the desulfurization method of the iron-alkali solution (complex iron) has larger limitation and has serious potential safety hazard. Therefore, for safety, we have not widely popularized the technology of desulfurizing an "iron-alkali solution" (i.e., a complex iron solution). In 1887, the process was carried out,russian scientist Sergei Winogradsky found that Beggiatoa (Beggiatoa) utilized hydrogen sulfide (H 2 S) as an energy source, CO 2 As a metabolic mechanism of carbon sources. After about 100 years, in 1984-1985, the study of the oxidation of wastewater sulfides with colorless sulfur oxidizing bacteria and oxygen in a dark environment by Cees Buisman of the netherlands was successful and achieved the purpose of sulfur recovery, but the study focused only on how to obtain extracellular elemental sulfur. Later, the research is mainly focused on the application research field of sewage deodorization, the THIOPAQ process technology is developed, the THIOPAQ technology is utilized to remove hydrogen sulfide in methane in 1992, and the application in the field of natural gas desulfurization is realized in Canada in 2002, but the technology generates a large amount of salt-containing wastewater in the actual application of natural gas desulfurization in China, the salt content in desulfurization liquid is increased, and the desulfurization efficiency is obviously reduced, so the technology is not widely popularized and applied in China.
Since 1995, the research team of the inventors of the present application has been working on the research in the field of gas biological desulfurization, and screened a strain of a thiophilic oxygen-consuming heat-resistant alkali-resistant bacterium named as "GDJ-3" from the soil of a salt lake in inner Mongolia, which has better homology with Alpha proteobacterrium sp (97%) and Ochrobactrum sp (98%). The bacteria has good desulfurization effect and can be widely applied to the fields of semi-water gas and shift gas desulfurization of synthetic ammonia in China. For this reason, we developed a "biochemical iron-alkali solution catalytic gas desulfurization method", and applied for the national invention patent and granted it on 09 in 2002, and subsequently, we studied GDJ-3 in more detail.
Later, the research of biological desulfurization in China is more and more hot, but remains in the theoretical research of laboratories, and large-scale industrialized application is not obtained. For example, the desulfurization mechanism of DS-3 strain (Rhodococcus erythropolis: rhodococcus erythropolis) was initially studied by university of south Kokai Ma Ting, and it was determined that the strain had final desulfurization rates of 64.08% and 85.86% for 08 diesel and refined diesel, respectively, and was capable of removing Dibenzothiophene (DBT) and DBT derivatives, while the removal ability for BT and BT derivatives was relatively poor. There are also many researchers who use rhodococcus erythropolis (Rhodococcus erythropolis), respectively,The studies of species such as thiobacillus ferrooxidans (Thiobacillus ferrooxidan), thiobacillus thiooxidans (Thiobacillus thiooxidan), gordonia sp.), pseudomonas sp, arthrobacter sp, desulphurized vibrio (Desulfovibrio desulfuricans), corynebacterium sp, brevibacterium sp, nocardia sp, paenibacillus polymyxa A11-2, mycobacterium grass Mycobacteriumphlei GTIS, paenibacillus sp, and acidi sp for removing DBT and DBT derivatives from petroleum and ores have not been carried out, but the studies have not been carried out on a large scale, nor has the effect of removing hydrogen sulfide and organic sulfur from gases. Some researchers have introduced the removal of H from natural gas using Thiobacillus ferrooxidans (Thobacillus ferrooxidans/Acidithiobacillus ferrooxidans) and Thiobacillus denitrificans (Thiobacillus denitrificans) 2 S, converting into elemental sulfur. Some researchers also reviewed the removal of H from gases using Thiobacillus thiofidobacter species (Thiobacillus thioparus) 2 S, forming intermediate products such as elemental sulfur, thiosulfate, dithionite, sulfite, sulfate and the like. Still other researchers reviewed the removal of H from gases using Thiobacillus thiooxidans species (Thiobacillus thiooxidans) 2 S, forming intermediate products such as elemental sulfur, thiosulfate, sulfate and the like. Several researchers reviewed the removal of H from gases with Xanthomonas sp 2 S, oxidizing into intermediate products such as elemental sulfur, thiosulfate, sulfate and the like. Some researchers also reviewed the removal of H from gases with Pseudomonas acidovorans (Pseudomonas acidovorans) 2 S, intermediate products such as elemental sulfur, thiosulfate, sulfate and the like are formed. Some researchers also reviewed the removal of H from gas by Pseudomonas putida (Pseudomonas putida) 2 S, intermediate products such as elemental sulfur, thiosulfate, sulfate and the like are formed. Some researchers also reviewed the removal of H from gases with mud green bacteria (Chlorobium limicola) 2 S, intermediate products such as elemental sulfur, thiosulfate, sulfate and the like are formed. Some researchers also reviewed the use of Mortierella furiosis (Thiomicrospira fris)ia) removal of H from gases by bacterial species 2 S, the sulfur is oxidized into elemental sulfur, and intermediate products such as thiosulfate, sulfate and the like are generated. Some researchers also reviewed the removal of H from gases using sulfur micro-spiro species (thiomicro spira sp.) 2 S, the sulfur is oxidized into elemental sulfur, and intermediate products such as thiosulfate, sulfate and the like are generated. Some researchers also reviewed the removal of H from gases with a strain of Sulfur-producing snow white (thiothiophanate) 2 S, the sulfur is oxidized into elemental sulfur, and intermediate products such as thiosulfate, sulfate and the like are generated. Some researchers also reviewed the removal of H from gases by bacteria such as Proteus (Hyphomicrobium sp.), rhizopus acidophilus (Chlorobium thiosulfatophilum), acidovorax (Prosthecochloris aestuarii), rhodospirillum salina (Halorhodospira abdelmalekii), microbacterium circulans (Thioalkalimicrobium cyclicum), thiobacillus natum (Thiobacillus neapolitanus), thiobacillus neotamium (Thiobacillus novellus), acer Bei Di Thiobacillus (Thiobacillus albertis), thiobacillus catabolicum (Thiobacillus pertabolis) 2 S, forming intermediate products such as thiosulfate, sulfate and the like besides elemental sulfur. Some researchers also reviewed the removal of H from gases by bacteria of the genus Alternaria (Thermothrix azorensis), alternaria microaerophilia (Thioalkalispira microaerophila), thiobacillus novellus, arthrobacter oxydans (Arthobacter oxydans), etc 2 S, intermediate products such as elemental sulfur, thiosulfate, sulfate and the like are formed. Some researchers also reviewed the removal of H from gases with bacteria such as Agrobacterium sp, bacillus sp, etc 2 S, elemental sulfur, thiosulfate, sulfate and other intermediate products. Some researchers also reviewed the removal of H from gases using Paracoccus versatile (Paracoccus versutus) 2 S, intermediate products such as elemental sulfur, thiosulfate, sulfate and the like are formed. Some researchers also reviewed the removal of H from gases using Chromobacterium (Chromatum), achromobacter (Achromobacter), desulfomonaum (Desulfomonas), mycobacterium (Mycobacterium), arthrobacter (Arthrobacter), flavobacterium (Flavobacterium), flavobacterium (Xanthobacterium), and the like 2 S, forming intermediate products such as elemental sulfur, thiosulfate, sulfate and the like. Some researchers also reviewed the removal of H from gases using thiobacillus thiodesis (Thiobacillus thiopams) and vibrio thiokallikrein (Thiolalkalivibrio) 2 S, intermediate products such as elemental sulfur, thiosulfate, sulfate and the like are formed. The theoretical research of removing sulfides in coke oven gas by Sphingomonas sp.PLI is carried out by Salix alba, but no practical application report is found. Enemy Rake reported that Alcaligenes faecalis strain M50-B1 (CGMCC No. 5219) was used as a desulfurizing and deodorizing agent. Yan Xiaojun et al report the use of Bacillus cereus strain ZJNB-B3 (accession number CCTCC No. M2016337) as a catalyst for the oxidation of inorganic sulfides. Zhiying et al report the removal of hydrogen sulfide from biogas by means of a strain of Parametric Bengalensis (Paracoccus bengaiensis) (CGMCC No. 13320). These bacterial desulfurization have a common feature of "oxidative conversion of hydrogen sulfide to elemental sulfur, and simultaneously, by-production of thiosulfate, sulfite, and sulfate". Therefore, after desulfurization with these bacteria, as the concentration of byproducts such as sulfate, thiosulfate, dithionite, sulfite and the like in the desulfurization liquid gradually increases, desulfurization efficiency gradually decreases, and when the concentration reaches a saturated state, crystallization such as sulfate and the like also occurs, and thus, clogging of the apparatus occurs.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides halomonas and application thereof in desulfurization. Absorbing hydrogen sulfide and/or organic sulfur in sulfur-containing gas by using a desulfurizing liquid containing halomonas; the biological desulfurization solution absorbing hydrogen sulfide and/or organic sulfur is oxidized and regenerated by air, and sulfur is produced as a byproduct, and the regenerated biological desulfurization solution is recycled.
The halomonas of the invention has the following classification status: proteobacteria (Proteobacteria)/gamma-Proteobacteria (gamma-Proteobacteria)/marine spirobacteria (Oceanospirillales)/Halomonadaceae (Halomonadaceae)/halomonad (Halomonas).
The strain of the halomonas provided by the invention is as follows: heterohalomonas (Halomonas aestuarii) HTYS003CGMCC No.25157, halophila (Halomonas alkalicola) HTYS004 CGMCC No.24747, halophila (Halomonas alkalicola) HTYS005 CGMCC No.25021, halophila (Halomonas alkalicola) HTYS006 CGMCC No.25022, chromium reduction halophila (Halomonas chromatireducens) HT008 CGMCC No.25158, halophila (Halomonas hydrothermalis) HTYS009 CGMCC No.25023, halophila (Halomonas lactosivorans) HTYS010 CGMCC No.25024 Monomonas mongolica (Halomonas mongoliensis) HTYS011 CGMCC No.25159, monomonas mongolica (Halomonas mongoliensis) HTYS012 CGMCC No.25160, monomonas mongolica (Halomonas mongoliensis) HTYS013 CGMCC No.25025, salomonas Halomonas (Halomonas salina) HTYS014 CGMCC No.25161, fan Shi Salomonas (Halomonas ventosae) HTYS0015 CGMCC No.25026, fan Shi Salomonas (Halomonas ventosae) HTYS016 CGMCC No.24757 or Monomonas mongolica (Halomonas mongoliensis) HTYS017 CGMCC No.24758. The strain is sent to China general microbiological culture collection center (CGMCC) for preservation, the preservation address is North Xielu No.1, no. 3 in the Korean area of Beijing, and the preservation date and the preservation number are shown in Table 1.
TABLE 1 Salmonella
The invention also provides the use of halomonas in the desulfurization of hydrogen sulfide and/or organic sulfur containing gases;
preferably, the halomonas is one or more of the strains described in table 1;
most preferably, the halomonas is an equal volume and equal concentration mix of the 14 strains described in table 1.
The invention also provides a desulfurization method, wherein the gas containing hydrogen sulfide and/or organic sulfur is passed through a solution containing halomonas.
In the invention, the desulfurization bacteria can be directly added into the desulfurization liquid of the existing desulfurization process to directly prepare biological desulfurization liquid for desulfurization; the spores of the desulphurizing bacteria can be directly added into the desulfurizing liquid of the prior desulfurizing process, and the spores of the desulphurizing bacteria can grow into bacteria gradually in the desulfurizing process, and then the desulfurizing effect is achieved.
Preferably, the halomonas is one or more of the strains described in table 1;
further preferably, the halomonas is an equal volume and equal concentration mixture of 14 strains as described in table 1.
Preferably, the solution is an alkaline solution; the pH value of the alkali liquor is more than or equal to 7 and less than or equal to 9; as a further preference, the lye is an aqueous solution containing ammonia and/or containing organic amines and/or containing sodium carbonate and/or containing sodium hydroxide and/or containing potassium hydroxide. The pH value of the biological desulfurization liquid is kept to be in the range of 7-9 in order to prevent acid-base corrosion of equipment.
The invention does not limit the bacterial concentration of the halomonas, and can play a certain desulfurizing effect only by adding the halomonas, but in order to make the desulfurizing effect prominent, the bacterial concentration of the halomonas in the solution is not less than 1 multiplied by 10 2 Each ml is preferably 1X 10 6 -1×10 10 And each mL.
The invention has no strict limitation on the process conditions, and can adopt normal pressure absorption, negative pressure absorption or pressurized absorption; for example, in the present application, an example of an actual application is the selection of absorption under pressurized conditions for desulfurization.
Preferably, after desulfurization, the solution containing halomonas is aerated with air/oxygen to regenerate the halomonas and produce sulfur as a byproduct.
Preferably, the desulfurization solution regeneration of the halophilic monad is carried out under normal pressure; in the case of the regeneration under normal pressure, the regeneration temperature is not higher than 100 ℃, preferably 25 to 45 ℃.
Preferably, the sulfur-containing gas comprises natural gas, coke oven gas, oil field gas, blast furnace gas, city gas, synthetic ammonia semi-water gas and shift gas, synthetic waste gas of dye plants, blow-down gas of chemical fiber plants or biogas; and/or
The total sulfur content in the sulfur-containing gas is less than 99.9% by volume.
The invention has no special requirement 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 percent (volume ratio).
Earlier studies by the inventors of the present application show that the halomonas of the present invention may be obtained by directly swallowing a sulfur-containing compound into a bacterial body, then performing aerobic digestion, and converting the digested sulfur into elemental sulfur; for convenience of description, the present invention uses the following general principles in which the sulfur-removing bacteria are expressed as follows:
when the gas contacts with biological desulfurization liquid, 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’
CS in the above reaction 2 COS, R-SH, R-S-R' are, respectively, carbon disulphide, carbon oxysulfide (carbonyl sulfide), mercaptans and thioethers, which belong to the class of volatile organic sulphur compounds.
The biological desulfurization liquid having absorbed sulfide is hereinafter referred to as "rich liquid". The rich liquid is oxidized and regenerated by air under the action of the desulphurisation 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 liquid after air oxidation regeneration is converted into lean liquid, and the lean liquid is recycled.
The invention mainly aims at the practicability of removing the sulfur-containing compounds in the gas, so that the method is directly applied to an actual production device, and the biological desulfurization liquid can be recycled as long as the method 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 intensively.
Compared with the traditional wet desulfurization method, the method has the following advantages: (1) for the traditional wet desulfurization method, when the total salt (thiosulfate and sulfate) content in the desulfurization liquid is more than 300g/L, the desulfurization efficiency is drastically reduced, the desulfurization efficiency cannot be improved by adding a large amount of catalyst, the desulfurization liquid is replaced and discharged in a large amount, and the desulfurization efficiency can be stabilized only when the total salt content is controlled below 300 g/L; the practice shows that the total salt content in the biological desulfurization liquid of the halomonas desulfurization method disclosed by the invention can not reduce the desulfurization efficiency when the total salt content reaches 500 g/L; (2) the traditional wet desulfurization method can be used for desulfurization under alkaline conditions, and the halomonas desulfurization method can be used for desulfurization under alkaline conditions or slightly acidic conditions; (3) the traditional wet desulfurization method basically has no capability of removing organic sulfur, and the halomonas of the invention has certain capability of removing organic sulfur; (4) while the conventional wet desulfurization method cannot economically maintain high desulfurization efficiency for a long time, the method for desulfurizing halomonas of the present invention can economically maintain high desulfurization efficiency for a long time.
The method for desulfurizing the halomonas has wide industrial application, can be used for desulfurizing natural gas, and can also be used for desulfurizing coke oven gas, oilfield gas, blast furnace gas, urban gas, synthetic ammonia semi-water gas and shift gas, synthetic waste gas of a dye factory, blow-down gas of a chemical fiber factory, biogas and other industrial raw material gas or waste gas containing hydrogen sulfide and organic sulfur, wherein the total sulfur content in the sulfur-containing gas is less than 99.9 percent (volume ratio).
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a schematic diagram of a laboratory desulfurization test apparatus.
Fig. 2 is a schematic diagram of a forced-air regeneration process for pressurized absorption in accordance with an embodiment.
Detailed Description
The following examples facilitate a better understanding of the present invention, but are not intended to limit the same. The experimental methods in the following examples are conventional methods unless otherwise specified. The test materials used in the examples described below, unless otherwise specified, were purchased from conventional Biochemical reagents. The quantitative tests in the following examples were all set up in triplicate and the results averaged.
Example 1
The inventor mixes the hot spring water obtained from the hot spring mouth of Beijing Chang Ping Xiaoshang mountain, condensed water of natural gas well of petrochemical large cattle and soil of Qinghai salt lake, carries out culture, enrichment, separation and purification, carries out desulfurization and domestication to obtain 14 halomonas strains with desulfurization capability, and sends the 14 halomonas strains to China general microbiological culture collection center (CGMCC) for collection, wherein the collection address is North Chen West road No.1 and No. 3 in the Yangqing district of Beijing city, and strain information and specific collection information are shown in Table 1.
The proliferation culture medium formula of the 14 halomonas strains is as follows: basic salt component (g/L): mgSO (MgSO) 4 ·7H 2 O,0.15;Na 2 S 2 O 3 ·5H 2 O,10.0;Na 2 HPO 4 ·12H 2 O,10.6;KH 2 PO 4 ,1.5;NH 4 Cl,0.4; 0.2g/L Yeast extract (Yeast extract) and trace element liquid TES were added at 1mL/L. With Na 2 CO 3 The pH was adjusted to 9.0. And (5) filtering and sterilizing.
Wherein the trace element liquid component (g/L): znSO (ZnSO) 4 ·7H 2 O,10.0;CuSO 4 ·5H 2 O,1.0;MnSO 4 ·4H 2 O,1.0;CoSO 4 ·7H 2 O,1.0;Cr 2 (SO 4 ) 3 ·15H 2 O,0.5;Na 2 B 4 O 7 ·10H 2 O,0.5;Na 2 MoO 4 ·2H 2 O,0.5;NaVO 3 ,0.1;pH 2.0(3M H 2 SO 4 )。
The proliferation culture conditions are as follows: culturing at 45deg.C under 150 r/min.
After studying these strains, it was found that 7 strains of halophila HTYS005 (Halomonas alkalicola HTYS) and halophila HTYS006 (Halomonas alkalicola HTYS) and lactose halophila HTYS010 (Halomonas lactosivorans HTYS 010) and mongolia HTYS011 (Halomonas mongoliensis HTYS 011), mongolia HTYS012 (Halomonas mongoliensis HTYS 012) and mongolia HTYS013 (Halomonas mongoliensis HTYS 013) and Fan Shi mongolia HTYS0015 (Halomonas ventosae HTYS 0015) belong to new strains, and they have not been reported in the literature, so that the present inventors have made more intensive studies and identification.
The 16S rRNA sequences of these 7 strains were as follows:
the gene sequence of the halophila HTYS005 (Halomonas alkalicola HTYS 005) bacteria is as follows:
the gene sequence of the halophila HTYS006 (Halomonas alkalicola HTYS 006) bacteria is:
the gene sequence of the halophila lactis HTYS010 (Halomonas lactosivorans HTYS 010) bacteria is as follows:
the gene sequence of the Monomonas mongolica HTYS011 (Halomonas mongoliensis HTYS 011) bacteria is as follows:
the gene sequence of the Monomonas mongolica HTYS0012 (Halomonas mongoliensis HTYS 012) bacteria is:
the gene sequence of the Monomonas mongolica HTYS013 (Halomonas mongoliensis HTYS 013) bacteria is as follows:
the gene sequence of Fan Shi Salmonella HTYS0015 (Halomonas ventosae HTYS 0015) bacteria is:
the present inventors further conducted laboratory desulfurization experiments on the strains described in table 1 to examine the desulfurization effect of each strain.
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 bacterial liquid, 3 is a gas inlet, and 4 is a gas outlet.
Referring to fig. 1, the laboratory desulfurization screening test operates as follows: about 150ml of the bacterial liquid 2 was put into a 250ml glass absorption bottle 1Introducing hydrogen sulfide-containing gas (nitrogen gas contains about 10000ppm of hydrogen sulfide, the flow rate is controlled at 80 ml/min) from a gas inlet 3, introducing into an absorption bottle 1, and absorbing hydrogen sulfide by bacteria liquid 2 through a bacteria liquid 2 layer; the gas from which hydrogen sulfide was removed was flowed out of the gas outlet 4 and into an absorption bottle containing a blue iodine-containing starch solution, and if the blue iodine-containing starch solution became colorless, it was indicated that the bacterial liquid 2 was saturated with hydrogen sulfide, absorption was stopped, and the absorption time t (minutes) was recorded. Then, the bacteria liquid 2 saturated in absorption is regenerated, and the regeneration step is as follows: introducing air (the flow rate is controlled to be about 200 ml/min) from a gas inlet 3, entering an absorption bottle 1, and allowing bacteria liquid 2 layer absorbing hydrogen sulfide to pass through, wherein the hydrogen sulfide in the bacteria liquid 2 is metabolized into elemental sulfur by bacteria; the regenerated gas flows out from the gas outlet 4, is vented, and is regenerated for 30 minutes. The regenerated bacterial liquid 2 is used for absorbing hydrogen sulfide: the above absorption steps are still repeated; then repeating the regeneration steps, thus, absorbing and regenerating; again, absorption and regeneration, and then recording the absorption saturation time t, the pH before absorption (or the pH after regeneration), and the pH after absorption for each time. First, we conducted a blank experiment using a sodium carbonate solution having a concentration of about 3g/L as described above, and the results of the experiment for absorbing hydrogen sulfide by the blank solution are shown in Table 2. Then, 150ml of bacterial liquid 2 (bacterial concentration 10) was prepared by adding bacteria to 3g/L of sodium carbonate solution 6 ~10 7 The above experiment was repeated, the mixed bacterial solution was obtained by mixing 14 strains having the same test concentration in equal volume, the experimental results of hydrogen sulfide absorption by the 14 bacterial solutions and the mixed bacterial solution are shown in tables 3 to 17, and the bacterial concentrations in tables 3 to 17 are 10 6 -10 7 And each ml. (Note in particular that since the newly prepared 3g/L sodium carbonate solution had a high pH and was unstable, the initial absorption time was long, and therefore, the first few times of instability were not required, and only experimental data after slightly stabilizing the pH were used).
TABLE 2 150ml sodium carbonate solution at 3g/L, H in gas 2 S content is 9995ppm, and when the flow is 80ml/min, the saturated experiment result is absorbed
TABLE 3 desulfurization solution composed of the salt monad HTYS003 bacteria in Table 1 was added to 150ml of sodium carbonate solution having a concentration of 3g/L, H in the gas 2 S content is 10000ppm, and when the flow is 80ml/min, the saturated test result is absorbed
Absorption times | pH before absorption (or after regeneration) | pH after absorption | Saturation time t (minutes) |
1 st time | 8.85 | 8.84 | 15.5 |
2 nd time | 8.87 | 8.86 | 17 |
3 rd time | 8.84 | 8.83 | 14 |
Fourth time | 8.86 | 8.85 | 16 |
5 th time | 8.88 | 8.87 | 12.5 |
Last time (6) | 8.89 | 8.88 | 14.5 |
The 7 th time | 8.90 | 8.89 | 15 |
8 th time | 8.91 | 8.90 | 17.5 |
Last time 9 | 8.92 | 8.91 | 16.5 |
10 th time | 8.91 | 8.91 | 13 |
11 th time | 8.93 | 8.92 | 14 |
12 th time | 8.94 | 8.93 | 14.5 |
13 th time | 8.96 | 8.95 | 13.5 |
The 14 th time | 8.97 | 8.96 | 15.2 |
15 th time | 8.99 | 8.98 | 13 |
The 16 th time | 8.99 | 8.97 | 14 |
The 17 th time | 8.99 | 8.98 | 14.2 |
TABLE 4 desulfurization solution composed of the bacterium HTYS004 of Salmonella enterica in TABLE 1 was added to 150ml of sodium carbonate solution having a concentration of 3g/L, H in the gas 2 S content is 10000ppm, and when the flow is 80ml/min, the saturated test result is absorbed
Absorption times | pH before absorption (or after regeneration) | pH after absorption | Saturation time t (minutes) |
1 st time | 8.86 | 8.84 | 16 |
2 nd time | 8.84 | 8.83 | 14 |
3 rd time | 8.85 | 8.84 | 13 |
Fourth time | 8.87 | 8.85 | 13.5 |
5 th time | 8.80 | 8.77 | 11.5 |
Last time (6) | 8.79 | 8.78 | 10.5 |
The 7 th time | 8.85 | 8.83 | 13 |
8 th time | 8.80 | 8.78 | 12.5 |
Last time 9 | 8.81 | 8.79 | 9.5 |
10 th time | 8.85 | 8.83 | 12 |
11 th time | 8.89 | 8.88 | 13 |
12 th time | 8.89 | 8.87 | 13.5 |
13 th time | 8.89 | 8.87 | 14.5 |
The 14 th time | 8.88 | 8.86 | 13.2 |
15 th time | 8.89 | 8.88 | 14 |
The 16 th time | 8.87 | 8.85 | 12 |
The 17 th time | 8.89 | 8.88 | 13.2 |
TABLE 5 desulfurization solution composed of the halophila HTYS005 bacteria of TABLE 1, H in gas, was added to 150ml of sodium carbonate solution having a concentration of 3g/L 2 S content is 10000ppm, and when the flow is 80ml/min, the saturated test result is absorbed
Absorption times | pH before absorption (or after regeneration) | pH after absorption | Saturation time t (minutes) |
1 st time | 8.93 | 8.92 | 17 |
2 nd time | 8.91 | 8.90 | 16 |
3 rd time | 8.90 | 8.91 | 15 |
Fourth time | 8.99 | 8.97 | 16 |
5 th time | 8.98 | 8.98 | 15.5 |
Last time (6) | 8.90 | 8.89 | 13.5 |
The 7 th time | 8.89 | 8.89 | 13 |
8 th time | 8.90 | 8.90 | 13.5 |
Last time 9 | 8.90 | 8.91 | 12.5 |
10 th time | 8.92 | 8.91 | 13 |
11 th time | 8.94 | 8.94 | 13 |
12 th time | 8.96 | 8.95 | 13.5 |
13 th time | 8.97 | 8.96 | 14 |
The 14 th time | 8.97 | 8.97 | 13 |
15 th time | 8.98 | 8.97 | 14.5 |
The 16 th time | 8.98 | 8.98 | 13.5 |
The 17 th time | 8.99 | 8.98 | 15 |
TABLE 6 desulfurization solution composed of the bacteria of the genus halophila HTYS006 of TABLE 1, H in gas, was added to 150ml of a sodium carbonate solution having a concentration of 3g/L 2 S content is 10000ppm, and when the flow is 80ml/min, the saturated test result is absorbed
Absorption times | pH before absorption (or after regeneration) | pH after absorption | Saturation time t (minutes) |
1 st time | 8.83 | 8.82 | 15 |
2 nd time | 8.82 | 8.81 | 13 |
3 rd time | 8.81 | 8.80 | 14 |
Fourth time | 8.79 | 8.80 | 13 |
5 th time | 8.83 | 8.81 | 12.5 |
Last time (6) | 8.79 | 8.80 | 13.5 |
The 7 th time | 8.85 | 8.85 | 13 |
8 th time | 8.87 | 8.85 | 12.5 |
Last time 9 | 8.82 | 8.80 | 13.5 |
10 th time | 8.84 | 8.82 | 13 |
11 th time | 8.84 | 8.83 | 14 |
12 th time | 8.86 | 8.85 | 13 |
13 th time | 8.88 | 8.87 | 13.5 |
The 14 th time | 8.88 | 8.87 | 13.2 |
15 th time | 8.89 | 8.86 | 13.3 |
The 16 th time | 8.88 | 8.87 | 13.5 |
The 17 th time | 8.89 | 8.88 | 14 |
TABLE 7 desulfurization solution composed of the bacteria HTYS008 of the chromium salt reducing uniconas in TABLE 1 was added to 150ml of a sodium carbonate solution having a concentration of 3g/L, H in the gas 2 S content is 10000ppm, and when the flow is 80ml/min, the saturated test result is absorbed
TABLE 8 desulfurization solution composed of Salmonella typhimurium HTYS009 bacteria in TABLE 1 was added to 150ml of sodium carbonate solution having a concentration of 3g/L, H in the gas 2 S content is 10000ppm, and when the flow is 80ml/min, the saturated test result is absorbed
Absorption times | pH before absorption (or after regeneration) | pH after absorption | Saturation time t (minutes) |
1 st time | 8.83 | 8.80 | 17 |
2 nd time | 8.82 | 8.81 | 15.5 |
3 rd time | 8.81 | 8.80 | 16 |
Fourth time | 8.83 | 8.82 | 16 |
5 th time | 8.85 | 8.83 | 15.5 |
Last time (6) | 8.83 | 8.81 | 16.5 |
The 7 th time | 8.82 | 8.80 | 15.5 |
8 th time | 8.81 | 8.79 | 15.5 |
Last time 9 | 8.83 | 8.81 | 14.5 |
10 th time | 8.85 | 8.84 | 14 |
11 th time | 8.87 | 8.85 | 14 |
12 th time | 8.88 | 8.86 | 13.5 |
13 th time | 8.88 | 8.87 | 13.5 |
The 14 th time | 8.88 | 8.89 | 13 |
15 th time | 8.89 | 8.88 | 12.5 |
The 16 th time | 8.89 | 8.87 | 12 |
The 17 th time | 8.90 | 8.88 | 12.5 |
TABLE 9 desulfurization solution composed of the bacteria HTYS010 of the salt-forming Pseudomonas lactobions in TABLE 1 was added to 150ml of a sodium carbonate solution having a concentration of 3g/L, H in the gas 2 S content is 9995ppm, and when the flow is 80ml/min, the saturated experiment result is absorbed
Absorption times | pH before absorption (or after regeneration) | pH after absorption | Saturation time t (minutes) |
1 st time | 8.72 | 8.71 | 16.5 |
2 nd time | 8.82 | 8.73 | 12 |
3 rd time | 8.75 | 8.75 | 16 |
Fourth time | 8.76 | 8.76 | 12.5 |
5 th time | 8.77 | 8.76 | 12.5 |
Last time (6) | 8.78 | 8.77 | 17.5 |
The 7 th time | 8.78 | 8.78 | 13 |
8 th time | 8.79 | 8.79 | 11 |
Last time 9 | 8.81 | 8.81 | 13.5 |
10 th time | 8.83 | 8.84 | 16.6 |
11 th time | 8.84 | 8.84 | 14.5 |
12 th time | 8.86 | 8.86 | 15 |
13 th time | 8.87 | 8.86 | 15.5 |
The 14 th time | 8.87 | 8.87 | 15.7 |
15 th time | 8.88 | 8.87 | 15.5 |
The 16 th time | 8.88 | 8.88 | 16.7 |
The 17 th time | 8.89 | 8.89 | 16.2 |
Table 10A desulfurization solution composed of the bacteria HTYS011 of Mongolian salt monad in Table 1 was added to 150ml of a sodium carbonate solution having a concentration of 3g/L, and H was contained in the gas 2 S content is 9995ppm, and when the flow is 80ml/min, the saturated experiment result is absorbed
Table 11A desulfurization solution composed of the bacteria HTYS012 of Mongolian salt monad in Table 1 was added to 150ml of a sodium carbonate solution having a concentration of 3g/L, and H was contained in the gas 2 S content is 9995ppm, and when the flow is 80ml/min, the saturated experiment result is absorbed
Absorption times | pH before absorption (or after regeneration) | pH after absorption | Saturation time t (minutes) |
1 st time | 8.81 | 8.80 | 16.5 |
2 nd time | 8.83 | 8.82 | 12 |
3 rd time | 8.85 | 8.83 | 16 |
Fourth time | 8.84 | 8.81 | 12.5 |
5 th time | 8.86 | 8.84 | 12.5 |
Last time (6) | 8.83 | 8.81 | 17.5 |
The 7 th time | 8.82 | 8.80 | 13 |
8 th time | 8.87 | 8.85 | 11 |
Last time 9 | 8.89 | 8.88 | 13.5 |
10 th time | 8.88 | 8.87 | 16.6 |
11 th time | 8.87 | 8.86 | 14.5 |
12 th time | 8.89 | 8.88 | 15 |
13 th time | 8.90 | 8.89 | 15.5 |
The 14 th time | 8.91 | 8.89 | 15.7 |
15 th time | 8.92 | 8.89 | 15.5 |
The 16 th time | 8.91 | 8.86 | 16.7 |
The 17 th time | 8.92 | 8.88 | 16.2 |
150ml sodium carbonate solution with the concentration of 3g/L in Table 12 is added into desulfurization solution composed of Monomonas mongolica HTYS013 bacteria in Table 1, and H in the gas is added 2 S content is 9995ppm, flow isAbsorption saturation test results at 80ml/min
Absorption times | pH before absorption (or after regeneration) | pH after absorption | Saturation time t (minutes) |
1 st time | 8.75 | 8.71 | 18.0 |
2 nd time | 8.80 | 8.73 | 16 |
3 rd time | 8.76 | 8.74 | 15 |
Fourth time | 8.75 | 8.73 | 14.5 |
5 th time | 8.76 | 8.71 | 15.5 |
Last time (6) | 8.78 | 8.77 | 17.5 |
The 7 th time | 8.77 | 8.77 | 13 |
8 th time | 8.79 | 8.79 | 11 |
Last time 9 | 8.82 | 8.81 | 13.5 |
10 th time | 8.83 | 8.81 | 16.6 |
11 th time | 8.84 | 8.83 | 14.5 |
12 th time | 8.85 | 8.83 | 15.5 |
13 th time | 8.87 | 8.86 | 16 |
The 14 th time | 8.87 | 8.85 | 16.7 |
15 th time | 8.89 | 8.87 | 16.5 |
The 16 th time | 8.90 | 8.88 | 16.7 |
The 17 th time | 8.89 | 8.87 | 16.5 |
TABLE 13 desulfurization solution composed of the salt monad HTYS014 bacteria of TABLE 1 was added to 150ml of sodium carbonate solution having a concentration of 3g/L, H in the gas 2 S content is 9995ppm, and when the flow is 80ml/min, the saturated experiment result is absorbed
Table 14A solution of 3g/L sodium carbonate in 150ml was added to the solution of Fan Shi of the bacteria of the genus Salmonella HTYS0015 of Table 1Sulfur liquid, H in gas 2 S content is 9995ppm, and when the flow is 80ml/min, the saturated experiment result is absorbed
Absorption times | pH before absorption (or after regeneration) | pH after absorption | Saturation time t (minutes) |
1 st time | 8.62 | 8.61 | 13.5 |
2 nd time | 8.72 | 8.71 | 14 |
3 rd time | 8.75 | 8.73 | 16 |
Fourth time | 8.76 | 8.76 | 12.5 |
5 th time | 8.76 | 8.76 | 12.5 |
Last time (6) | 8.75 | 8.66 | 17.5 |
The 7 th time | 8.68 | 8.66 | 13 |
8 th time | 8.69 | 8.69 | 11 |
Last time 9 | 8.71 | 8.70 | 13.5 |
10 th time | 8.73 | 8.70 | 16.5 |
11 th time | 8.74 | 8.73 | 14.5 |
12 th time | 8.76 | 8.74 | 15 |
13 th time | 8.77 | 8.73 | 15.5 |
The 14 th time | 8.77 | 8.72 | 16 |
15 th time | 8.78 | 8.75 | 14.5 |
The 16 th time | 8.77 | 8.73 | 15.7 |
The 17 th time | 8.78 | 8.75 | 15.5 |
TABLE 15 desulfurization solution composed of Fan Shi Salmonella HTYS016 bacteria in TABLE 1, H in gas, was added to 150ml of sodium carbonate solution having a concentration of 3g/L 2 S content is 9995ppm, and when the flow is 80ml/min, the saturated experiment result is absorbed
Absorption times | pH before absorption (or after regeneration) | pH after absorption | Saturation time t (minutes) |
1 st time | 8.72 | 8.71 | 16 |
2 nd time | 8.82 | 8.72 | 12 |
3 rd time | 8.75 | 8.70 | 16 |
Fourth time | 8.75 | 8.75 | 12.5 |
5 th time | 8.76 | 8.76 | 12.5 |
Last time (6) | 8.78 | 8.71 | 17.5 |
The 7 th time | 8.77 | 8.76 | 13 |
8 th time | 8.76 | 8.77 | 11 |
Last time 9 | 8.83 | 8.81 | 13.5 |
10 th time | 8.87 | 8.83 | 16.6 |
11 th time | 8.84 | 8.82 | 14.5 |
12 th time | 8.87 | 8.84 | 15 |
13 th time | 8.87 | 8.83 | 16 |
The 14 th time | 8.87 | 8.82 | 16.5 |
15 th time | 8.88 | 8.86 | 15.5 |
The 16 th time | 8.85 | 8.82 | 16.5 |
The 17 th time | 8.89 | 8.86 | 15.5 |
150ml sodium carbonate solution with the concentration of 3g/L in Table 16 is added into desulfurization solution composed of Monomonas mongolica HTYS017 bacteria in Table 1, and H in the gas 2 S content is 9995ppm, and when the flow is 80ml/min, the saturated experiment result is absorbed
Absorption times | pH before absorption (or after regeneration) | pH after absorption | Saturation time t (minutes) |
1 st time | 8.72 | 8.71 | 13.5 |
2 nd time | 8.82 | 8.80 | 14 |
3 rd time | 8.85 | 8.80 | 16.5 |
Fourth time | 8.83 | 8.83 | 12 |
5 th time | 8.82 | 8.82 | 12 |
Last time (6) | 8.81 | 8.75 | 18.5 |
The 7 th time | 8.87 | 8.86 | 13.5 |
8 th time | 8.85 | 8.85 | 12 |
Last time 9 | 8.84 | 8.83 | 13 |
10 th time | 8.86 | 8.80 | 17 |
11 th time | 8.83 | 8.82 | 13.5 |
12 th time | 8.85 | 8.82 | 15.5 |
13 th time | 8.87 | 8.84 | 15.5 |
The 14 th time | 8.86 | 8.82 | 16.5 |
15 th time | 8.87 | 8.86 | 15.5 |
The 16 th time | 8.86 | 8.83 | 15.5 |
The 17 th time | 8.85 | 8.82 | 15 |
TABLE 17 desulfurization solution of mixed bacterial solution composed of the above 14 bacteria of the genus Halomonas (Halomonas) was added to 150ml of sodium carbonate solution having a concentration of 3g/L, H in the gas 2 S content is 9995ppm, and when the flow is 80ml/min, the saturated experiment result is absorbed
Absorption times | pH before absorption (or after regeneration) | pH after absorption | Saturation time t (minutes) |
1 st time | 8.86 | 8.85 | 68 |
2 nd time | 8.87 | 8.86 | 25.5 |
3 rd time | 8.87 | 8.87 | 18.5 |
Fourth time | 8.90 | 8.89 | 27 |
5 th time | 8.93 | 8.92 | 36 |
Last time (6) | 9.0 | 8.99 | 48 |
The 7 th time | 9.05 | 9.02 | 72.5 |
From the above experimental data, it is known that the time for absorbing hydrogen sulfide with only 3g/L concentration of sodium carbonate solution is long initially, but as the number of absorption-regeneration increases, the absorption saturation time gradually shortens, and eventually stabilizes between 3 and 4 minutes, and the ability of pure water to absorb hydrogen sulfide does not differ much. However, after adding a single species of Halomonas (Halomonas) to a 3g/L sodium carbonate solution, the final absorption saturation time of the desulfurization solution was stabilized between 11 and 18.5 minutes, which is 4 times the absorption saturation time of a pure 3g/L sodium carbonate solution.
In the same manner, when mixed bacterial solutions of 14 strains of Halomonas (Halomonas) are added into a 3g/L concentration sodium carbonate solution, the saturated time for absorbing hydrogen sulfide reaches more than 18.5 minutes, and even the saturated time is reduced and then increased with the increase of the absorption-regeneration times until reaching 72.5 minutes, which is more than 18 times of the absorption saturated time of a pure 3g/L concentration sodium carbonate solution.
The above coarse-step screening experiment proves that the experimental effect of the mixed bacterial liquid is better than that of a single bacterial strain.
Example 2
The present inventors further conducted desulfurization production experiments directly using mixed bacterial liquids (mixed bacterial liquids are mixed in equal volumes with 14 bacterial liquids having the same concentration) of these 14 strains of Halomonas (Halomonas) in table 1 on a desulfurization device of a natural gas desulfurization station of Daniu land # 1, division of middle petrochemical north.
An embodiment is shown in fig. 2.
Fig. 2 is a schematic diagram of a forced-air regeneration process for pressurized absorption in accordance with an embodiment. Wherein, 1 natural gas before desulfurization, 2 a pressurizing desulfurization tower, 3 natural gas after desulfurization, 4 lean solution, 5 rich solution, 6 flash tank, 7 flash steam, 8 a regeneration tower, 9 lean solution tank, 10 desulfurization pump, 11 sulfur foam, 12 vent air, 13 sulfur foam tank, 14 sulfur foam pump, 15 filter, 16 sulfur paste, 17 filtrate, 18 air, 19 high pressure blower.
Referring to fig. 2, natural gas 1 before desulfurization enters from the bottom of a pressurized desulfurization tower 2 and is in countercurrent contact with lean liquid 4 sprayed on the top; the sulfur-containing compound in the natural gas 1 before desulfurization is absorbed by the lean solution 4, the absorption pressure is about 3.5MPa, the natural gas 1 before desulfurization is converted into the natural gas 3 after desulfurization, and the natural gas flows out from the top of the pressurized desulfurization tower 2; the lean solution 4 absorbed with the sulfur-containing compounds is converted into the rich solution 5 at the bottom of the pressurized desulfurizing tower 2; the rich liquid 5 flows out from the bottom of the pressurized desulfurization tower 2, enters a desulfurization liquid flash tank 6, is depressurized to about 0.6MPa, releases flash gas 7 for recycling, meanwhile, the rich liquid 5 after the flash vaporization depressurization is automatically pressed into a regeneration tower 8 from the bottom, air 18 enters the regeneration tower 8 from the bottom after being pressurized by a high-pressure blower 19, in the regeneration tower 8, the rich liquid 5 and the air 18 are fully mixed, sulfur-containing compounds in the rich liquid 5 are metabolized into elemental sulfur by bacteria through oxygen to form sulfur foam 11, the rich liquid 5 is converted into lean liquid 4, and the lean liquid 4 automatically flows into a lean liquid tank 9 from a lean liquid overflow port of the regeneration tower 8, and then is sent into the pressurized desulfurization tower 2 for desulfurization after being pressurized by a desulfurization pump 10; meanwhile, the formed sulfur foam 11 is floated to the top of the regeneration tower 8, then overflows to the sulfur foam tank 13 automatically, is sent to the filter 15 by the sulfur foam pump 14 for filtering, and is filtered to obtain sulfur paste 16 and filtrate 17, wherein the sulfur paste 16 can be sold as a byproduct, and the filtrate 17 flows into the lean liquid tank 9 for recycling; the air 18 becomes the vent air 12 and is released to the outside.
In the embodiment, we carried out a natural gas desulfurization test on a desulfurization device of a natural gas desulfurization station # 1 of Daku Di Bos of China petrochemical company, the desulfurization process of the desulfurization station is pressurized absorption (absorption pressure is 3.5 MPa), and forced air blowing regeneration flow is carried out. The implementation flow is shown in fig. 2, and the equipment specifications and parameters are shown in table 18.
Table 18 specifications of the respective devices in embodiment one
Apparatus and method for controlling the operation of a device | Specification (mm) | Quantity of | Remarks |
Pressurized desulfurizing tower (2) | DN2200×12000 | 1 | |
Flash tank (6) | DN1400×8200 | 1 | |
Regeneration tower (8) | DN2000×(8000+3000) | 1 | |
Lean liquid tank (9) | DN2500L=6000 | 1 | |
Desulfurization pump (10) | Q=60m 3 /h,H=450,110kw | 2 | Open one by one |
Sulfur foam trough (13) | DN1400,H=2000 | 1 | |
Sulfur foam pump (14) | Q=15m 3 /h,H=60,5.5 |
2 | Open one by one |
Filter (15) | Filtration area 100m 2 ,5.5kw | 1 | |
High-pressure air blower (19) | Q=600Nm 3 /h, |
2 | Open one by one |
Before the end of 10 months in 2020, the enterprise adopts a complex iron desulfurization method to carry out desulfurization, and potassium hydroxide (KOH) is used as an alkali source. After the end of 10 months in 2020, the enterprise adopts the Halomonas (Halomonas) desulfurization method (hereinafter referred to as a DDS method) to carry out desulfurization, and takes 30% alkali liquor (NaOH) as an alkali source. The inventors of the present application stopped the addition of complex iron and potassium hydroxide (KOH) to the desulfurization liquid in the desulfurization apparatus of the forced-air regeneration flow path in the existing pressurized absorption (absorption pressure is 3.5 MPa), then directly added the desulfurization bacteria and 30% alkali solution (NaOH), and controlled the bacterial concentration in the desulfurization liquid to 1X 10 6 ~1×10 10 And (3) carrying out industrial desulfurization test per mL.
Under the same conditions, the results of desulfurization by the iron complex method and desulfurization by the DDS method are shown in table 18, which are obtained by comparison with the same natural gas desulfurization apparatus. From the operation condition, under the same condition, the desulfurization efficiency of the DDS method is higher than that of the complex iron method, the DDS method is not blocked, and the complex iron method can cause equipment blocking phenomenon about 1 month each time. The comprehensive benefit of the DDS method is far greater than that of the complex iron method.
Table 19 the operation of DDS desulfurization and complex iron desulfurization were compared as follows:
operating parameters and operating conditions | DDS method | Complex iron method |
Daily throughput of natural gas (ten thousand Nm) 3 /d) | 3.6~8.4 | 3.6~8.4 |
H in natural gas 2 S content (g/Nm) 3 ) | 4~12 | 4~12 |
Circulation amount of desulfurization solution (m) 3 /h) | 28 | 50 |
H in natural gas after desulfurization 2 S content (g/Nm) 3 ) | 0 to 20 (most of which cannot be detected) | 10~80 |
Desulfurizing liquid pH value | 6.5~8.6 | 9~10 |
Daily consumption of alkali (kg/d) | 25~75(NaOH) | 150~300(KOH) |
Daily amount of desulfurizing agent (kg/d) | 14 (DDS bacteria)Agents and culture Medium | 150-250 (Complex iron medicament) |
Equipment blockage condition | Never is blocked | Blocking for about 1 month |
The total salt content in the desulfurizing liquid is more than 300g/L, and the desulfurizing efficiency is changed | The desulfurization efficiency is unchanged and is still more than 99 percent | Down to 80% or less |
The total salt content in the desulfurizing liquid is more than 500g/L, and the desulfurizing efficiency is changed | The desulfurization efficiency is unchanged and is still more than 99 percent | Down to 60% or less |
When the pH value of the desulfurization solution is lower than 6, the desulfurization efficiency is changed | The desulfurization efficiency is unchanged and is still more than 99 percent | Down to 60% or less |
Mercaptan removal rate | More than 99 percent | Less than 30% |
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The halomonas is characterized in that: the Salmonella is Heterophylla (Halomonas aestuarii) HTYS003CGMCC No.25157, alkaleidosomonas (Halomonas alkalicola) HTYS004 CGMCC No.24747, alkaleidosomonas (Halomonas alkalicola) HTYS005 CGMCC No.25021, alkaleidosomonas (Halomonas alkalicola) HTYS006 CGMCC No.25022, salmonella chromium (Halomonas chromatireducens) HTYS008 CGMCC No.25158, cellomonas thermofluid (Halomonas hydrothermalis) HTYS009 CGMCC No.25023, salmonella lactose (Halomonas lactosivorans) HTYS010 CGMCC No.25024, monomonas mongolica (Halomonas mongoliensis) HTYS011 CGMCC No.25159, monomonas (Halomonas mongoliensis) HTYS 25160, monomonas (Halomonas mongoliensis) HT013 CGMCC No.25025, salmonella (omonas) HTYS014 CC No.25161, salmonella Fan Shi (Halomonas ventosae) HTYS0015 CGMCC No. Fan Shi) HTCC No. 0173 or Monomonas (Halomonas salt).
2. Use of halomonas for the desulfurization of hydrogen sulfide and/or organic sulfur containing gases;
preferably, the halomonas is one or more of the strains of claim 1;
most preferably, the halomonas is an equal volume and equal concentration blend of 14 strains as described in claim 1.
3. A desulfurization method, characterized in that: the hydrogen sulfide and/or organic sulfur containing gas is passed through a solution containing halomonas.
4. A desulfurization method according to claim 3, characterized in that: said halomonas is one or more of the strains described in claim 1;
preferably, the halomonas is an equal volume and equal concentration mixture of 14 strains according to claim 1.
5. The desulfurization method according to claim 3 or 4, characterized in that: the solution is alkali liquor; preferably, the pH value of the alkali liquor is more than or equal to 7 and less than or equal to 9; preferably, the lye is an aqueous solution containing ammonia and/or organic amine and/or sodium carbonate and/or sodium hydroxide and/or potassium hydroxide.
6. The desulfurization method according to claim 5, characterized in that: the bacteria concentration of Salmonella in the solution is not less than 1×10 2 Each ml is preferably 1X 10 6 -1×10 10 And each mL.
7. A desulfurization method according to claim 3, characterized in that: absorption under normal pressure and/or pressure conditions is selected for desulfurization.
8. A desulfurization method according to claim 3, characterized in that: after desulfurization, air/oxygen is introduced into the solution containing the halomonas to regenerate the halomonas and produce sulfur as a byproduct.
9. The desulfurization method according to claim 8, characterized in that: regenerating the desulfurizing liquid containing salt monad under normal pressure; in the case of the regeneration under normal pressure, the regeneration temperature is not higher than 100 ℃, preferably 25 to 45 ℃.
10. A desulfurization method according to claim 3, characterized in that: the sulfur-containing gas comprises natural gas, coke oven gas, oilfield gas, blast furnace gas, city gas, synthetic ammonia semi-water gas, shift gas, synthetic waste gas of dye plants, and blow-down gas or biogas of chemical fiber plants; and/or
The total sulfur content in the sulfur-containing gas is less than 99.9% by volume.
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