CN102935330B - Biological activated carbon (BAC) and method for removing H2S in oil storage tank in oil field by utilizing same - Google Patents

Biological activated carbon (BAC) and method for removing H2S in oil storage tank in oil field by utilizing same Download PDF

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CN102935330B
CN102935330B CN201210441972.5A CN201210441972A CN102935330B CN 102935330 B CN102935330 B CN 102935330B CN 201210441972 A CN201210441972 A CN 201210441972A CN 102935330 B CN102935330 B CN 102935330B
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activated carbon
carbon
bacterium liquid
post
formula
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CN102935330A (en
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刘永军
刘孝坤
张爱宁
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Xian University of Architecture and Technology
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Abstract

The invention discloses BAC and a method for removing H2S in an oil storage tank in an oil field by utilizing the same to remove the H2S polluting gas in the oil storage tank in the oil field effectively. The BAC is formed by activated carbon modified by a sodium hydroxide solution and sulphate oxidizing bacteria absorbed on the modified activated carbon. When the BAC is used for removing the H2S gas in the oil storage tank, a device filled with the BAC is placed at the port of the oil storage tank, the H2S in the oil storage tank is removed by using the absorption of the modified activated carbon and degradation of microbes, the H2S absorbed by the modified activated carbon can serve as a nutrient matrix of the microbes in the removing process, therefore the activated carbon can maintain a high removing efficiency to the H2S within a relative long time without regeneration.

Description

A kind of bioactive carbon and utilize it to remove H in oil field oil storage tank 2the method of S
Technical field
The invention discloses a kind of bioactive carbon and utilize H in this biologically active carbon removal oil field oil storage tank 2the method of S.
Background technology
Biological activated carbon is after carrier enriched microorganism, can form biomembrane take granular activated carbon; suction-operated by biomembranous biodegradation and active carbon can be removed pollutant; the while biomembrane also part pollutant of biodegradable charcoal absorption makes regenerating active carbon, thereby has greatly extended the life cycle of active carbon.But the application of biological activated carbon mainly concentrates on the purified treatment field of drinking water at present.
Along with the development of petrochemical industry, the odor pollution of petroleum chemical enterprise is day by day serious, and the foul gas harm that particularly contains hydrogen sulfide is more remarkable.The method of removing hydrogen sulfide generally adopts physical-chemical process, as absorption method, absorption process, oxidizing process etc.Although these methods are widely used in industrial production in the world, and have accumulated rich experience,, they all exist, and investment is large, high energy consumption and produce the shortcomings such as secondary pollution, does not meet environmental requirement.Field produces is distinguished and is furnished with many large-scale oil storage tanks, the H discharging in tank 2physical and mental health and the surrounding environment of S to field personnel caused serious harm.But, also there is no a kind of special effective workaround for oil field oil storage tank hydrogen sulfide contamination at present.
Summary of the invention
One of object of the present invention is to provide a kind of bioactive carbon, and this bioactive carbon is mainly used in removing the hydrogen sulfide in dusty gas.
For this reason, bioactive carbon provided by the invention, this bioactive carbon comprises modified activated carbon and is adsorbed on the oxide sulfate bacterium on modified activated carbon, it is characterized in that, described bioactive carbon adopts following method preparation:
Step 1, prepare modified activated carbon:
The NaOH solution that is 20% with mass fraction by dried active carbon soaked after 24 hours, and the activated carbon at 110 ℃ of temperature after dry immersion makes modified activated carbon;
Step 2, seed selection oxide sulfate bacterium:
(1) activated sludge of taking from sewage treatment plant's returned sludge is joined to fluid nutrient medium M 1in after under 30 ℃ of constant temperatures vibration cultivate 3～5 days, obtain bacterium liquid, wherein: activated sludge and fluid nutrient medium M 1volume ratio be 1:10;
Described fluid nutrient medium M 1formula be:
Distilled water: 100mL;
Na 2S 2O 3：0.5g；
NH 4Cl：0.01g；
Na 2HPO 4·12H 2O：0.05g；
MgCl 2·6H 20：0.02g；
NaHCO 3：0.1g；
(2) by bacterium liquid at enrichment nutrition base M 2in continuously switching cultivate until the absorbance of nutrient solution is 0.6～0.8 o'clock, the nutrient solution of gained is oxide sulfate bacterium liquid; In switching cultivation process, be linked into for the first time enrichment nutrition base M 2in bacterium liquid to be cultivated be the bacterium liquid that step (1) obtains, be linked into enrichment nutrition base M later at every turn 2in bacterium liquid the to be cultivated bacterium liquid that is last round of cultivation, and, each added bacterium liquid to be cultivated and enrichment nutrition base M 2volume ratio be: 1:9; Each vibration under 30 ℃ of conditions cultivated the absorbance that detects afterwards nutrient solution for 3～5 days;
Described enrichment nutrition base M 2formula be:
Distilled water: 100mL;
Na 2S 2O 3：1g、
NH 4Cl：0.2g、
K 2HPO 4：0.3g、
MgCl 2·6H 20：0.05g、
CaCl 2：0.02g；
PH is: 7 ± 0.5;
Step 3, modified activated carbon absorption oxide sulfate bacterium domestication:
First, modified activated carbon is filled in post;
Then, in the post that is filled with modified activated carbon, circulation dropping contains NaS 2oxide sulfate bacterium liquid, until the NaS of post efflux 2clearance A>=90%;
Then, contain H to passing into continuously in post 2the air of S gas is until the H in post Exhaust Gas 2s clearance B>=95%;
Finally, the filler in post being dried under 20-40 ℃ of condition to its moisture content is 30～40% to obtain bioactive carbon;
Wherein: NaS 2the calculating of clearance A is as shown in (formula 1):
A = C 0 - C ′ C 0 × 100 % (formula 1)
In (formula 1): C 0for containing NaS 2oxide sulfate bacterium liquid in NaS 2molar concentration; C' is NaS in post efflux 2molar concentration;
H 2the calculating of S clearance B is as shown in (formula 2):
B = g 0 - g ′ g 0 × 100 % (formula 2)
In (formula 2): g 0for the H in post import department gas 2the molar concentration of S; G' is H in post Exhaust Gas 2the molar concentration of S.
Preferably, the particle diameter of above-mentioned activated carbon is 0.5mm-1mm.
Preferably, the above-mentioned NaS that contains 2oxide sulfate bacterium liquid in NaS 2mass concentration is 5mg/L.
Preferably, the above-mentioned H that contains passing in post 2h in the air of S gas 2the concentration of S gas is 1mg/L, and throughput is 0.5L/min.
Bioactive carbon provided by the invention is a large amount of sulfur-oxidizing bacteria of growing in activated carbon surface and hole, utilizes modified activated carbon absorption H 2s and sulfur-oxidizing bacteria are to H 2s transforms the H in dusty gas 2s gas is removed, and its conversion reaction formula is as shown in (formula 3):
H 2s+O 2=H 2o+S(formula 3)
This biological activated carbon has H 2s has very strong absorption and conversion capability, to the H in dusty gas 2s has good removal efficiency.
Another object of the present invention is to provide H in a kind of above-mentioned biologically active carbon removal oil field oil storage tank 2the method of S, is specifically placed on oil field oil storage tank mouth by the device that is filled with bioactive carbon, utilizes bioactive carbon to adsorb the H in the gas of discharging from oil storage tank 2s, described bottom of device offers air admission hole.
Within every 1～2 month in removal process, on the bioactive carbon in device, spray nutrient solution, the formula of this nutrient solution is:
Distilled water: 100mL;
Na 2S 2O 3：0.5g；
NH 4Cl：0.01g；
Na 2HPO 4·12H 2O：0.05g；
MgCl 2·6H 20：0.02g；
NaHCO 3：0.1g。
Said apparatus is cylinder device, and described in this, the outer wall of cylinder device is provided with and takes ear; Described cylinder device top is provided with cover, and the sidewall of this cover offers steam vent.
Preferably, the filling thickness of bioactive carbon in above-mentioned cylinder device is 2/3rds of cylinder device height.
In oil field oil storage tank provided by the invention, the removal method of H2S has following feature:
(1) activated carbon modifiedly combine with microbiological treatment, under normal temperature condition, can reach the removal effect of good toxic and harmful, and effect is lasting.
(2) modified activated carbon can significantly improve toxic and harmful H 2the adsorption capacity of S, the H adsorbing 2s supplies with microorganism as nutrient matrix, makes microbial biofilm have stable matrix to supply with, and has improved H 2the removal effect of S, its clearance is more than 90%, makes like this activated carbon can maintain in a long time higher removal efficiency in the situation that not needing regeneration.
Accompanying drawing explanation
Below in conjunction with accompanying drawing and the specific embodiment, the present invention is described in further detail.
Fig. 1 is the structural representation of cylinder device.
The specific embodiment
The preparation method of bioactive carbon disclosed by the invention is: being filled with the post of modified activated carbon, (internal diameter is 5cm, and in the lucite post of high 30cm or other vessel, circulation drips and contains NaS 2oxide sulfate bacterium liquid, until the NaS of post efflux 2clearance A>=90% then passes into continuously and contains H according to the throughput of 0.5L/min in post 2air (the H of S gas 2the concentration of S is 1mg/L) tame H in test column Exhaust Gas 2when S clearance B>=95%, biological activated carbon domestication finishes; Make its moisture content obtain bioactive carbon 30～40% by dry under 20～40 ℃ of conditions the filler in post.Wherein: contain NaS 2oxide sulfate bacterium liquid in NaS 2mass concentration is 5mg/L; NaS 2the calculating of clearance A is as shown in (formula 1):
A = C 0 - C ′ C 0 × 100 % (formula 1)
In formula: C 0for containing NaS 2oxide sulfate bacterium liquid in NaS 2molar concentration; C' is NaS in post efflux 2molar concentration;
H 2the calculating of S clearance B is as shown in (formula 2):
B = g 0 - g ′ g 0 × 100 % (formula 2)
In (formula 2): g 0for H in post import department gas 2the molar concentration of S; G' is H in post Exhaust Gas 2the molar concentration of S.
NaS in method 2the detection of molar concentration adopts the P-aminodimethylaniline colorimetric method in GB/T5750.5-2006; H 2the detection of S molar concentration adopts gas chromatography.
Modified activated carbon in method is to be that the NaOH solution that 0.5mm～1mm dried active carbon mass fraction is 20% soaked after 24 hours by particle diameter, the dry modified activated carbon making at 110 ℃ of temperature.
Oxide sulfate bacterium liquid is the oxide sulfate bacterium liquid that adopts following seed selection cultural method to obtain:
(1) activated sludge of taking from sewage treatment plant's returned sludge is joined to fluid nutrient medium M 1in after under 30 ℃ of constant temperatures vibration cultivate 3～5 days, obtain bacterium liquid, wherein: activated sludge and fluid nutrient medium M 1volume ratio be 1:10;
Fluid nutrient medium M used 1formula be:
Distilled water: 100mL;
Na 2S 2O 3：0.5g；
NH 4Cl：0.01g；
Na 2HPO 4·12H 2O：0.05g；
MgCl 2·6H 20：0.02g；
NaHCO 3：0.1g；
(2) by bacterium liquid at enrichment nutrition base M 2in continuously switching cultivate until the absorbance of nutrient solution is 0.6～0.8 o'clock, the nutrient solution of gained is oxide sulfate bacterium liquid; Transferring in cultivation process continuously, be linked into for the first time enrichment nutrition base M 2in bacterium liquid to be cultivated be the bacterium liquid that step (1) obtains, be linked into enrichment nutrition base M later at every turn 2in bacterium liquid the to be cultivated bacterium liquid that is last round of cultivation, and, each added nutrient solution and enrichment nutrition base M for the treatment of 2volume ratio be: 1:9; Each vibration under 30 ℃ of conditions cultivated the absorbance of utilizing spectrophotometer detection nutrient solution after 3～5 days;
Described enrichment nutrition base M 2formula be:
Distilled water: 100mL;
Na 2S 2O 3：1g、
NH 4Cl：0.2g、
K 2HPO 4：0.3g、
MgCl 2·6H 20：0.05g、
CaCl 2：0.02g；
PH is: 7 ± 0.5.
The present invention is by active carbon is carried out to modification, and is combined with microbial, forms a kind of modified activated carbon-biofilm system, and this system can be to low concentration toxic and harmful H 2s maintains higher removal efficiency in long-time.Utilize this characteristic bioactive carbon disclosed by the invention for removing the H of oil field oil storage tank 2s, method is specially: the cylinder device that is filled with bioactive carbon is placed on to oil field oil storage tank mouth, utilizes bioactive carbon to adsorb the H in the gas of discharging from oil storage tank 2s, cylinder device bottom offers air admission hole 2.
In order to extend the service life of bioactive carbon, within every 1～2 month in removal process, on the bioactive carbon in cylinder device, spray nutrient solution, the formula of this nutrient solution is:
Distilled water: 100mL;
Na 2S 2O 3：0.5g；
NH 4Cl：0.01g；
Na 2HPO 4·12H 2O：0.05g；
MgCl 2·6H 20：0.02g；
NaHCO 3：0.1g。
The filling thickness of bioactive carbon in cylinder device is 2/3rds of device height.
As shown in Figure 1, the outer wall of the present invention's cylinder device 1 used is provided with takes ear 3, to facilitate, device is placed on to oil storage tank mouth; In rainwater access to plant, device top is provided with cover 4, and offers steam vent 5 on the sidewall of this cover 4.
Embodiment 1:
The removal method of the preparation of the bioactive carbon of this embodiment and hydrogen sulfide gas is as follows:
Step 1, the preparation of modified activated carbon:
(1) be 0.5mm～1mm active carbon by particle diameter with ultra-pure water continuous washing for several times, under 110 ℃ of temperature conditions dry 6 hours for subsequent use;
(2) dry active carbon is placed in to 20%(mass fraction) NaOH solution soak after 24 hours, at 110 ℃ of temperature dry 12 hours, obtain modified activated carbon after cooling;
Step 2, the seed selection of oxide sulfate bacterium and cultivation:
(1) from sewage treatment plant (north, Xi'an stone bridge sewage treatment plant) returned sludge, get 10mL activated sludge and join 100mL fluid nutrient medium M 1in, under 30 ℃ of constant temperatures, the constant temperature oscillator dynamic cultivation of rotating speed 121r/min, cultivates 5 days, obtains bacterium liquid;
(2) by 360mL enrichment nutrition base M 2equivalent is sub-packed in sterilizing 30min in four 250mL triangular flasks, in a triangular flask wherein, add the bacterium liquid obtaining in 10mL step (1), under 30 ℃ of constant temperatures, the constant temperature oscillator dynamic cultivation of rotating speed 121r/min, cultivate the absorbance that detects nutrient solution after 4 days with spectrophotometer, now absorbance is less than 0.6, then drawing previous nutrient solution 10mL with aseptic absorption tube moves in another triangular flask, switching three times so continuously, obtain the oxide sulfate bacterium liquid that nutrient solution absorbance is 0.7, be placed in 4 ℃ of refrigerators for subsequent use.
Step 3, the preparation of bioactive carbon:
(1) in the post that is filled with modified activated carbon, circulation dropping contains NaS 2oxide sulfate bacterium liquid, until the NaS of post efflux 2clearance A>=90%, wherein: contain NaS 2oxide sulfate bacterium liquid in NaS 2mass concentration is 5mg/L;
(2) Xiang Zhuzhong passes into continuously and contains H according to the throughput of 0.5L/min 2air (the H of S gas 2the gas concentration of S is 1mg/L) tame H in test column Exhaust Gas 2when S clearance B>=95%, biological activated carbon domestication finishes;
(3) filler in post is at room temperature dry, make its moisture content 30～40%, obtain bioactive carbon.
Step 4, H 2the removal effect of S gas detects:
(1) in the device shown in Fig. 1, fill respectively biological activated carbon described in modified activated carbon, step 3 (3) described in common active carbon, step 2 (2) described in the step 2 (1) of equivalent, for H 2the test of S removal effect;
(2) pass into continuously and contain H to being filled with in the device of active carbon respectively 2the air of S gas, controls import H 2s concentration is 0.5～1mg/L, and gas flow is 0.3～0.5L/min, detects and imports and exports gas H by gas chromatography 2the concentration of S, calculates H 2the clearance of S;
(3) adopt existing " charcoal absorption H 2s penetrates the assay method of capacity and time of break-through " (the coal industry standard MT/T1067-2008 of the People's Republic of China (PRC)) described method to common active carbon in this embodiment, modified activated carbon and biological activated carbon involved in the present invention to H 2s removal effect is analyzed, and result is as shown in table 1.
The common active carbon of table 1, modified activated carbon and biological activated carbon are to H 2s removal effect is analyzed
Figure GDA0000465047200000091
Testing result shows, adopts the inventive method to adsorb significantly better than simple common active carbon or modified activated carbon the removal effect of hydrogen sulfide.The present invention is simple to operate, to environment non-secondary pollution, is easy to industrial production, to field produces district H 2the solution of S pollution problem has important practical significance.

Claims (8)

1. a bioactive carbon, this bioactive carbon comprises modified activated carbon and is adsorbed on the oxide sulfate bacterium on modified activated carbon, it is characterized in that, described bioactive carbon adopts following method preparation:
Step 1, prepare modified activated carbon:
The NaOH solution that is 20% with mass fraction by dried active carbon soaked after 24 hours, and the activated carbon at 110 ℃ of temperature after dry immersion makes modified activated carbon;
Step 2, seed selection oxide sulfate bacterium:
(1) activated sludge of taking from sewage treatment plant's returned sludge is joined to fluid nutrient medium M 1in after under 30 ℃ of constant temperatures vibration cultivate 3～5 days, obtain bacterium liquid, wherein: activated sludge and fluid nutrient medium M 1volume ratio be 1:10;
Described fluid nutrient medium M 1formula be:
Distilled water: 100mL;
Na 2S 2O 3：0.5g；
NH 4Cl：0.01g；
Na 2HPO 4·12H 2O：0.05g；
MgCl 2·6H 20：0.02g；
NaHCO 3：0.1g；
(2) by bacterium liquid at enrichment nutrition base M 2in continuously switching cultivate until the absorbance of nutrient solution is 0.6～0.8 o'clock, the nutrient solution of gained is oxide sulfate bacterium liquid; In switching cultivation process, be linked into for the first time enrichment nutrition base M 2in bacterium liquid to be cultivated be the bacterium liquid that step (1) obtains, be linked into enrichment nutrition base M later at every turn 2in bacterium liquid the to be cultivated bacterium liquid that is last round of cultivation, and, each added bacterium liquid to be cultivated and enrichment nutrition base M 2volume ratio be: 1:9; Each vibration under 30 ℃ of conditions cultivated the absorbance that detects afterwards nutrient solution for 3～5 days;
Described enrichment nutrition base M 2formula be:
Distilled water: 100mL;
Na 2S 2O 3：1g、
NH 4Cl：0.2g、
K 2HPO 4：0.3g、
MgCl 2·6H 20：0.05g、
CaCl 2：0.02g；
PH is: 7 ± 0.5;
Step 3, modified activated carbon absorption oxide sulfate bacterium domestication:
First, modified activated carbon is filled in post;
Then, in the post that is filled with modified activated carbon, circulation dropping contains NaS 2oxide sulfate bacterium liquid, until the NaS of post efflux 2clearance A>=90%;
Then, contain H to passing into continuously in post 2the air of S gas is until the H in post Exhaust Gas 2s clearance B>=95%;
Finally, the filler in post being dried under 20-40 ℃ of condition to its moisture content is 30～40% to obtain bioactive carbon;
Wherein: NaS 2the calculating of clearance A is as shown in (formula 1):
A = C 0 - C ′ C 0 × 100 % (formula 1)
In (formula 1): C 0for containing NaS 2oxide sulfate bacterium liquid in NaS 2molar concentration; C' is NaS in post efflux 2molar concentration;
H 2the calculating of S clearance B is as shown in (formula 2):
B = g 0 - g ′ g 0 × 100 % (formula 2)
In (formula 2): g 0for the H in post import department gas 2the molar concentration of S; G' is H in post Exhaust Gas 2the molar concentration of S.
2. bioactive carbon as claimed in claim 1, is characterized in that, the particle diameter of described activated carbon is 0.5mm～1mm.
3. bioactive carbon as claimed in claim 1, is characterized in that, described in contain NaS 2oxide sulfate bacterium liquid in NaS 2mass concentration is 5mg/L.
4. bioactive carbon as claimed in claim 1, is characterized in that, described in pass into the H that contains in post 2h in the air of S gas 2the concentration of S gas is 1mg/L, and throughput is 0.5L/min.
5. H in the biologically active carbon removal oil field oil storage tank utilizing described in claim 1 2the method of S, is characterized in that, the device that is filled with bioactive carbon is placed on to oil field oil storage tank mouth, utilizes bioactive carbon to adsorb the H in the gas of discharging from oil storage tank 2s, described bottom of device offers air admission hole.
6. method as claimed in claim 5, is characterized in that, within every 1～2 month in removal process, on the bioactive carbon in device, sprays nutrient solution, and the formula of this nutrient solution is:
Distilled water: 100mL;
Na 2S 2O 3：0.5g；
NH 4Cl：0.01g；
Na 2HPO 4·12H 2O：0.05g；
MgCl 2·6H 20：0.02g；
NaHCO 3：0.1g。
7. method as claimed in claim 5, is characterized in that, described device is cylinder device, and described in this, the outer wall of cylinder device is provided with and takes ear; Described cylinder device top is provided with cover, and the sidewall of this cover offers steam vent.
8. method as claimed in claim 7, is characterized in that, the filling thickness of bioactive carbon in cylinder device is 2/3rds of cylinder device height.
CN201210441972.5A 2012-11-07 2012-11-07 Biological activated carbon (BAC) and method for removing H2S in oil storage tank in oil field by utilizing same Expired - Fee Related CN102935330B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0523812B2 (en) * 1988-01-15 1993-04-05 Dowa Mining Co
CN101058055A (en) * 2007-06-01 2007-10-24 哈尔滨工业大学 Biologically deodorizing method
CN101200698A (en) * 2007-11-26 2008-06-18 宁波工程学院 Microorganism synchronously removing ammonia and sulfureted hydrogen foul gas and method for preparing the same
CN102050516A (en) * 2009-10-27 2011-05-11 中国石油化工股份有限公司 Method for preparing selective microbial packing

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0523812B2 (en) * 1988-01-15 1993-04-05 Dowa Mining Co
CN101058055A (en) * 2007-06-01 2007-10-24 哈尔滨工业大学 Biologically deodorizing method
CN101200698A (en) * 2007-11-26 2008-06-18 宁波工程学院 Microorganism synchronously removing ammonia and sulfureted hydrogen foul gas and method for preparing the same
CN102050516A (en) * 2009-10-27 2011-05-11 中国石油化工股份有限公司 Method for preparing selective microbial packing

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