CN103184175B - Microbial strain for natural gas purification and application - Google Patents
Microbial strain for natural gas purification and application Download PDFInfo
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- CN103184175B CN103184175B CN201110456646.7A CN201110456646A CN103184175B CN 103184175 B CN103184175 B CN 103184175B CN 201110456646 A CN201110456646 A CN 201110456646A CN 103184175 B CN103184175 B CN 103184175B
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- natural gas
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- hydrogen sulfide
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000003345 natural gas Substances 0.000 title claims abstract description 23
- 230000000813 microbial effect Effects 0.000 title claims abstract description 13
- 238000000746 purification Methods 0.000 title claims abstract description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 25
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 241000605118 Thiobacillus Species 0.000 claims abstract description 13
- 241000605214 Thiobacillus sp. Species 0.000 claims abstract 2
- 241000894006 Bacteria Species 0.000 claims description 27
- 230000001580 bacterial effect Effects 0.000 claims description 17
- 230000003750 conditioning effect Effects 0.000 claims description 10
- 239000002054 inoculum Substances 0.000 claims description 5
- 238000012258 culturing Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000011081 inoculation Methods 0.000 abstract description 2
- 230000003044 adaptive effect Effects 0.000 abstract 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 239000005864 Sulphur Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 244000005700 microbiome Species 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 3
- 241001052560 Thallis Species 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 241001509286 Thiobacillus denitrificans Species 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 230000035479 physiological effects, processes and functions Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 description 1
- 238000003794 Gram staining Methods 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- GWZOLWLJEJRQMZ-UHFFFAOYSA-N [S].S Chemical group [S].S GWZOLWLJEJRQMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011218 seed culture Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004879 turbidimetry Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention relates to a microbial strain for purifying natural gas and application thereof; the strain belongs to the genus Thiobacillus, is named as (Thiobacillus sp.TYY-1), is preserved in China Center for Type Culture Collection (CCTCC) and has a strain number (CCTCC NO: M2010282); the temperature range of the microbial strain adaptive to growth is 15-45 ℃, the pH range of the microbial strain adaptive to growth is 6.0-9.0, and the inoculation amount in the process of enlarged culture is 10%; the strain, and the passage strain, the variant strain and the derivative strain which retain the active strain are applied to natural gas purification treatment; the concentration of hydrogen sulfide in the feed gas is lower than 40g/m3When in use, the hydrogen sulfide removal rate of the strains reaches 100 percent; the concentration of hydrogen sulfide in the feed gas is lower than 80g/m3When the method is used, the hydrogen sulfide removal rate of the strains is higher than 95%; has higher purification capability to hydrogen sulfide in natural gas.
Description
Technical field
The present invention relates to a kind of microbial strains for natural gas conditioning and application, and retain the strain of going down to posterity of this active bacteria, variant and the application of derivative strain in selexol process.
Background technology
From current domestic natural gas exploratory development present situation, increasing dispersion sulfur-containing gas needs process.From economic target and treatment effect Comprehensive Assessment, when latent sulfur content is less than 0.1t/d, dry desulfurization is comparatively applicable; When latent sulfur content is greater than 50t/d, amine method+claus process just can fully demonstrate economic benefit; When latent sulfur content occupy therebetween, mode ideal at home and abroad at present often adopts liquid-phase oxidation reduction and desulfurization technology to process.But the main drawback of liquid-phase oxidation reduction is chemical cost height and sulphur easily occurs to block up, and also have the generation of industrial effluent, this certainly will cause the increase of running cost and the decline of sulphur analysis.
By comparison, biological desulfurization process just compensate for above-mentioned deficiency, and it utilizes the metabolic process of microorganism to carry out desulfurization, neither needs expensive treatment soln and catalyzer therebetween, does not also process the discharge of waste in a large number.At the alkali that absorption process consumes, acted in bio-reactor by microorganism catalysis and recovered, reduce the consumption of chemical; The sulphur generated has wetting ability, and not easily cause sulphur to block up, hydrophilic sulphur also can do agrochemical and sterilant, improves added value.Further, when new block gas pool reserve is difficult to clear and definite, selects the biological desulfurizing technology being easy to move, supporting general facilities is few to carry out pilot production and there is many advantages.
The beginning of the eighties in last century, NKK Jing Bin make when utilizing the sweetening power of thiobacillus ferrooxidant (Thiobacillus ferrooxidans) to define Bio-SR technique for the treatment of Crouse's unstripped gas, at unstripped gas H
2s content 0.5g/m
3and 1.0g/m
3h
2s decreasing ratio reaches 99.99%, and the hydrogen sulfide content in processed gas, at below 10ppm, shows good sweetening effectiveness.In recent years, what Sichuan University Zhang Yongkui, Shandong University Zheng officers and people, Hebei University of Technology's residence of a high official entered the people such as the Shen relevant H2S that utilized thiobacillus ferrooxidant to carry out removes research, achieves comparatively satisfied sweetening effectiveness.But the bacterial classification adopted in above-mentioned research is growth in sour environment all, between its pH value range 2-4.Obviously for being all acid H
2s gas, in selexol process, is difficult to arrive satisfied purification rate.Thus, have no this type of bacterial classification technique to report in Sweet natural gas biological desulphurization.
The nineties Holland Paques company and Shell company developed jointly a kind of new industrial gasses biological desulfurizing technology, utilize thiobacillus denitrificans (Thiobacillus denitrificans) in the basic conditions NaHS be oxidized to elementary sulfur, simultaneously alkali lye is able to recycling utilization.In September, 2002, this cover technique carried out the industrial application of gas conditioning first time in Canada, and the unstripped gas H2S content of device process is 0.2%, and the gas H2S content after process is less than 4 × 10
-6.End 2005, have 45 cover Shell-Paques process units in the world and come into operation, wherein have 4 covering devices local for natural gas purification processing in Canada, the U.S. etc. respectively.
Therefore, Sweet natural gas biological desulphurization be a kind of with the obvious advantage, meet Sustainable development requirement, tool Novel desulphurization technology with broad prospects for development.But the primary prerequisite of carrying out the research of Sweet natural gas biological desulfurization process is exactly the desulfurization microorganism of excellent.
Summary of the invention
The object of this invention is to provide a kind of microbial strains for natural gas conditioning and application, this bacterial classification is that a strain can the novel bacterial of effective elimination hydrogen sulfide in natural gas, with regard to its this Pseudomonas of Morphology and physiology biochemical property preliminary evaluation in Thiobacillus, called after (Thiobacillus sp TYY-1).This bacterial classification on November 3rd, 2010 in China typical culture collection center (be called for short CCTCC, address: in the Bayi Road Wuhan University of Hongshan District, Wuhan City of Hubei China province) preservation, preserving number: CCTCC NO:M2010282.
Invention also provides this bacterial classification Physiology and biochemistry character, the temperature range determining this bacterium Adaptable growth is 15-45 DEG C, and optimum growth temp is 30 DEG C, and the pH scope of Adaptable growth is 6.0-9.0, the pH value of optimum growh is 8.0, and the optimum inoculation amount in enlarged culturing process is 10%.In process of growth, be in lag phase at 0-20h t bacteria YY-1, this phase bacterial poor growth, is in logarithmic phase on 20-60h bacterium, the quick growth and breeding of this phase bacterial, and quantity increases by geometric progression, and after 60h, bacterium enters stationary phase and decline phase.
Present invention also offers the sweetening power evaluation of programme of this bacterial classification, shown in main flow, accompanying drawing 1.Unstripped gas is by gas distributor from lower to upper by absorption liquid, and purified gas is discharged from top, absorption tower, the liquid absorbing H2S by two position difference from absorption tower flow direction bioreactor.In bio-reactor, alkali lye and nutritive medium can be added by two pipelines receiving reactor middle and lower part.Air blasts bottom bio-reactor, forms gas lift reactive system, and the sulfide be simultaneously also oxidized in liquid phase for thiobacillus TYY-1 provides electron acceptor(EA) and gas lift power.Oxidation generate sulphur due to density difference come downwards to reactor bottom after enter settling bowl, settling bowl supernatant liquor rises to absorption tower tower top recycle by peristaltic pump.By analyze unstripped gas determine its sweetening power at the hydrogen sulfide content of absorption tower import and outlet, by determine this bacterial classification in unstripped gas concentration of hydrogen sulfide lower than 40g/m
3time, t bacteria YY-1 reaches 100% to hydrogen sulfide stripping.In unstripped gas, concentration of hydrogen sulfide is lower than 80g/m
3time, t bacteria YY-1 to hydrogen sulfide stripping higher than 95%.
Accompanying drawing explanation
Fig. 1 t bacteria YY-1 sweetening power evaluation experimental flow process.
Fig. 2 TYY-1 thalline photo under an optical microscope.
Fig. 3 solution ph is on the impact of TYY-1 thalli growth.
Fig. 4 solution temperature is on the impact of TYY-1 thalli growth.
Fig. 5 inoculum size is on the impact of TYY-1 thalli growth.
The growth curve of Fig. 6 TYY-1.
Fig. 7 TYY-1 is to the decreasing ratio of different concns hydrogen sulfide.
Embodiment
Embodiment 1: the separation andpreconcentration of bacterial classification
Gather the activated sludge of Southwest Oil production operation district sewage treatment plant.By domestication enrichment, get the bacterium liquid 1mL tamed, make the diluent of 10-1,10-2,10-3,10-4,10-5,10-6 concentration with sterilized water successively.Then by each for the diluent of 10-4,10-5,10-6 concentration 0.2mL, be inoculated into the upper of plate culture medium respectively, evenly, be inverted in biochemical cultivation case and cultivate, until white circular point-like small colonies appears in solid culture primary surface, this process needs 10-14d in coating.
Provoke the calcination on slide of white single bacterium colony, have obvious sulphur taste to produce.Examined under a microscope down by thalline, thalline size is 0.5 ~ 2.5 μm, single, in pairs, or short catenation, have crystal to exist in its cell visible under microscope, gramstaining is negative.On flat board, bacterium colony face shaping is circular, the bacterium colony of periphery white.In conjunction with " uncle Jie Shi Bacteria Identification hand then ", identify that the microorganism of acquisition is Thiobacillus (Thiobacillus).Accompanying drawing 2.
Embodiment 2: the impact that initial pH value grows t bacteria YY-1
Under investigating initial pH value of medium 5.0,6.0,7.0,8.0,9.0 and 10.0 condition, the growing state of TYY-1, result shows that thiobacillus TYY-1 is 8.0 time, and OD value is the highest, illustrates that microorganism growth is best.
Accompanying drawing 3.
Embodiment 3: the impact that temperature grows t bacteria YY-1
Under investigating 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C and 40 DEG C of temperature, the growing state of TYY-1, result shows that thiobacillus TYY-1 is 30 DEG C time, and OD value is the highest, illustrates that microorganism growth is best.Accompanying drawing 4.
Embodiment 4: the impact that inoculum size grows t bacteria YY-1
Investigating inoculum size is under the condition of 5%, 10%, 15% and 20%, and the growing state of TYY-1, result shows that the OD value of thiobacillus TYY-1 10% time is the highest, illustrates that microorganism growth is best.Accompanying drawing 5.
The growth cycle of embodiment 5: t bacteria YY-1 is investigated
Inoculum size according to 10% by microbionation in the fresh culture (initial pH value 8.0) of certain volume, after fully cultivating at 30 DEG C, every certain hour section, adopt the bacterium amount in turbidimetry timing mensuration nutrient solution, and incubation time corresponding with it for surveyed OD value is mapped, obtain the growth curve of this bacterium.From growth curve, be in lag phase at 0-20h t bacteria YY-1, this phase bacterial poor growth, is in logarithmic phase on 20-60h bacterium, the quick growth and breeding of this phase bacterial, and quantity increases by geometric progression, and after 60h, bacterium enters stationary phase and decline phase.Accompanying drawing 6.
The sweetening power evaluation of embodiment 6: t bacteria YY-1
TYY-1 access is equipped with in the triangular flask of 500mL seed culture medium, 30 DEG C, cultivates under 150rpm condition, nutrient solution is poured in the bio-reactor that 5000mL initial soln is housed after having cultivated, utilize peristaltic pump that solution is circulated in whole system.After level stability, in absorption tower, pass into civil natural gas provide trace sulfide for TYY-1 grows.After TYY-1 growth completely, passing into concentration of hydrogen sulfide is respectively 20g/m
3, 40g/m
3, 60g/m
3and 80g/m
3sweet natural gas as unstripped gas, measure hydrogen sulfide sulfur-bearing in purified gas, calculate its decreasing ratio, determine the sweetening power of TYY-1, sweetening power evaluation rubric is shown in Fig. 1.Experimental result as shown in Figure 7, TYY-1 in unstripped gas concentration of hydrogen sulfide lower than 40g/m
3time, effect after 5 days its purification rate can reach 100%, be 60g/m removing concentration of hydrogen sulfide
3and 80g/m
3unstripped gas time, under current experiment condition, remain on more than 95% in effect 5 days after purification rates, demonstrate TYY-1 comparatively strong to the ability that removes of hydrogen sulfide in natural gas, there is potential industrial application value.
Claims (6)
1. the microbial strains for natural gas conditioning, it is characterized in that: this bacterium classification called after thiobacillus TYY-1 (Thiobacillus sp.TYY-1), at the deposit number of China typical culture collection center (CCTCC) is: CCTCC NO:M2010282.
2. as claimed in claim 1 for the microbial strains CCTCC NO:M2010282 of natural gas conditioning, it is characterized in that: the temperature range that this growth adapts to is 15-45 DEG C.
3. as claimed in claim 1 for the microbial strains CCTCC NO:M2010282 of natural gas conditioning, it is characterized in that: the pH value that this growth is suitable for is between 6.0-9.0.
4., as claimed in claim 1 for the microbial strains CCTCC NO:M2010282 of natural gas conditioning, it is characterized in that: the inoculum size of this bacterial classification in enlarged culturing process is 10%.
5. the microbial strains CCTCC NO:M2010282 for natural gas conditioning according to claim 1 applies, and it is characterized in that: this bacterial classification and retain the strain of going down to posterity of this active bacteria, variant and derivative strain and can be applied to natural gas purification processing;
Described bacterial classification is thiobacillus TYY-1.
6. the microbial strains CCTCC NO:M2010282 for natural gas conditioning according to claim 1 applies as claimed in claim 5, it is characterized in that: this bacterial classification in unstripped gas concentration of hydrogen sulfide lower than 40g/m
3time, t bacteria YY-1 reaches 100% to hydrogen sulfide stripping rate; In unstripped gas, concentration of hydrogen sulfide is lower than 80g/m
3time, t bacteria YY-1 to hydrogen sulfide stripping rate higher than 95%.
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CN103184175B true CN103184175B (en) | 2015-08-19 |
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Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107118982B (en) * | 2017-05-05 | 2021-03-26 | 南京工业大学 | Thiobacillus ferrooxidans and application thereof |
CN108660091A (en) * | 2018-03-27 | 2018-10-16 | 常州赛尔斯生物科技有限公司 | A kind of mixed culture for removing hydrogen sulfide in H 2 S-containing gas |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5981266A (en) * | 1996-05-20 | 1999-11-09 | Gas Research Institute | Microbial process for the mitigation of sulfur compounds from natural gas |
CN1238711A (en) * | 1996-11-27 | 1999-12-15 | 帕克斯生物系统公司 | Process for biological removal of sulphide |
EP1161552A1 (en) * | 1999-03-18 | 2001-12-12 | Emil A.J. D.I. Wieser-Linhart | Method of obtaining methyl alcohol from raw gas and installation for carrying out said method |
CN2870960Y (en) * | 2006-01-18 | 2007-02-21 | 北京合百意生态能源科技开发有限公司 | Marsh-gas desulfurizer |
CN102250956A (en) * | 2011-06-15 | 2011-11-23 | 中国科学院广州能源研究所 | A method for preparing hydrogen-doped natural gas from biomass raw materials |
-
2011
- 2011-12-30 CN CN201110456646.7A patent/CN103184175B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5981266A (en) * | 1996-05-20 | 1999-11-09 | Gas Research Institute | Microbial process for the mitigation of sulfur compounds from natural gas |
CN1238711A (en) * | 1996-11-27 | 1999-12-15 | 帕克斯生物系统公司 | Process for biological removal of sulphide |
EP1161552A1 (en) * | 1999-03-18 | 2001-12-12 | Emil A.J. D.I. Wieser-Linhart | Method of obtaining methyl alcohol from raw gas and installation for carrying out said method |
CN2870960Y (en) * | 2006-01-18 | 2007-02-21 | 北京合百意生态能源科技开发有限公司 | Marsh-gas desulfurizer |
CN102250956A (en) * | 2011-06-15 | 2011-11-23 | 中国科学院广州能源研究所 | A method for preparing hydrogen-doped natural gas from biomass raw materials |
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